5-fluoropyrimidinone derivatives

ABSTRACT

This present disclosure is related to the field of 5-fluoropyrimidinones and their derivatives and to the use of these compounds as fungicides.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional PatentApplication Ser. No. 61/232,177 filed Aug. 7, 2009.

BACKGROUND AND SUMMARY OF THE INVENTION

Fungicides are compounds, of natural or synthetic origin, which act toprotect and/or cure plants against damage caused by agriculturallyrelevant fungi. Generally, no single fungicide is useful in allsituations. Consequently, research is ongoing to produce fungicides thatmay have better performance, are easier to use, and cost less.

The present disclosure relates to 5-fluoropyrimidinone compounds andtheir use as fungicides. The compounds of the present disclosure mayoffer protection against ascomycetes, basidiomycetes, deuteromycetes andoomycetes.

One embodiment of the present disclosure may include compounds ofFormula I:

wherein R¹ is:

-   -   H;    -   C₁-C₆ alkyl optionally substituted with 1-3 R⁴;    -   C₁-C₆ alkenyl optionally substituted with 1-3 R⁴;    -   C₃-C₆ alkynyl optionally substituted with 1-3 R⁴;    -   phenyl or benzyl wherein each of the phenyl or the benzyl may be        optionally substituted with 1-3 R⁵, or with a 5- or 6-membered        saturated or unsaturated ring system, or with a 5-6 fused ring        system, or with a 6-6 fused ring system each containing 1-3        heteroatoms wherein each ring may be optionally substituted with        1-3 R⁵, biphenyl or naphthyl optionally substituted with 1-3 R⁵;    -   -(CHR⁶)_(m)OR⁷;    -   —(CHR⁶)_(m)N(R⁹)R¹⁰;    -   —C(═O)R⁸;    -   —C(═S)R⁸;    -   —S(O)₂R⁸;    -   —C(═O)OR⁸;    -   —C(═S)OR⁸;    -   —(CHR⁶)_(m)N(R⁹)R¹⁰;    -   —C(═O)N(R⁹)R¹⁰; or    -   —C(═S)N(R⁹)R¹⁰;        wherein m is an integer 1-4;

R² is:

-   -   H; or    -   C₁-C₆ alkyl optionally substituted with R⁴;        alternatively R¹ and R² may be taken together to form:    -   ═CR¹¹N(R¹²)R¹³;

R³ is:

-   -   C₁-C₆ alkyl optionally substituted with 1-3 R⁴, C₁-C₆ haloalkyl,        C₁-C₆ hydroxyalkyl, C₂-C₆ alkoxyalkyl, C₂-C₆ haloalkoxyalkyl,        C₂-C₆ alkenyl optionally substituted with R¹⁴, C₂-C₆        haloalkenyl, C₃-C₆ alkynyl, phenyl or benzyl wherein each of the        phenyl or the benzyl may be optionally substituted with 1-3 R⁵,        or with a 5- or 6-membered saturated or unsaturated ring system,        or with a 5-6 fused ring system, or with a 6-6 fused ring system        each containing 1-3 heteroatoms wherein each ring may be        optionally substituted with 1-3 R⁵, biphenyl or naphthyl        optionally substituted with 1-3 R⁵;    -   -(CHR⁶)_(m)OR⁷;    -   —(CHR⁶)_(m)SR⁸; or    -   —(CHR⁶)_(m)N(R⁹)R¹⁰;        R⁴ is independently halogen, C₁-C₆ alkyl, C₁-C₄ haloalkyl, C₁-C₄        alkoxy, C₁-C₄ haloalkoxy, C₁-C₄ alkylthio, C₁-C₄ haloalkylthio,        amino, halothio, C₁-C₃ alkylamino, C₂-C₆ alkoxycarbonyl, C₂-C₆        alkylcarbonyl, C₂-C₆ alkylaminocarbonyl, hydroxyl, C₃-C₆        trialkylsilyl, phenyl optionally substituted with 1-3 R⁵, or        with a 5- or 6-membered saturated or unsaturated ring containing        1-3 heteroatoms wherein each ring may be optionally substituted        with 1-3 R⁵;        R⁵ is independently halogen, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₁-C₆        alkoxy, C₁-C₆ haloalkoxy, C₁-C₆ alkylthio, C₁-C₆ haloalkylthio,        halothio, amino, C₁-C₆ alkylamino, C₂-C₆ dialkylamino, C₂-C₆        alkoxycarbonyl, C₂-C₆ alkylcarbonyl, C₁-C₆ alkylsulfonyl, nitro,        hydroxyl, or cyano;        R⁶ is H, C₁-C₆ alkyl, C₁-C₆ alkoxy, C₁-C₆alkoxycarbonyl, phenyl        or benzyl wherein each of the phenyl or the benzyl may be        optionally substituted with 1-3 R⁵;        R⁷ is H, C₁-C₈ alkyl, C₂-C₆ alkenyl, C₃-C₆ alkynyl, C₁-C₆        haloalkyl, C₁-C₆ alkoxyalkyl, C₂-C₆ trialkylsilyl, C₂-C₆        trialkylsilylalkyl alkylcarbonyl, C₁-C₆ alkoxycarbonyl, phenyl        or benzyl wherein each of the phenyl or the benzyl may be        optionally substituted with 1-3 R⁵, or with a 5- or 6-membered        saturated or unsaturated ring system, or with a 5-6 fused ring        system, or with a 6-6 fused ring system each containing 1-3        heteroatoms wherein each ring may be optionally substituted with        1-3 R⁵, biphenyl or naphthyl optionally substituted with 1-3 R⁵;        R⁸ is H, C₁-C₆ alkyl, C₂-C₆ alkenyl, C₃-C₆ alkynyl, C₁-C₆        haloalkyl, C₁-C₆ alkoxyalkyl, phenyl or benzyl wherein each of        the phenyl or the benzyl may be optionally substituted with 1-3        R⁵, or with a 5- or 6-membered saturated or unsaturated ring        system, or with a 5-6 fused ring system, or with a 6-6 fused        ring system each containing 1-3 heteroatoms wherein each ring        may be optionally substituted with 1-3 R⁵, biphenyl or naphthyl        optionally substituted with 1-3 R⁵;        R⁹ is H, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₁-C₆ alkoxyalkyl, C₂-C₆        alkylcarbonyl, phenyl or benzyl wherein each of the phenyl or        the benzyl may be optionally substituted with 1-3 R⁵, or with a        5- or 6-membered saturated or unsaturated ring system, or with a        5-6 fused ring system, or with a 6-6 fused ring system each        containing 1-3 heteroatoms wherein each ring may be optionally        substituted with 1-3 R⁵, biphenyl or naphthyl optionally        substituted with 1-3 R⁵;        R¹⁰ is H, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₁-C₆ alkoxyalkyl, C₂-C₆        alkylcarbonyl, or benzyl, wherein the benzyl may be optionally        substituted with 1-3 R⁵;        alternatively R⁹ and R¹⁰ may be taken together to form a 5- or        6-membered saturated or unsaturated ring containing 1-3        heteroatoms wherein each ring may be optionally substituted with        1-3 R⁵;        R¹¹ is H or C₁-C₄ alkyl;        R¹² is H cyano, hydroxyl, C₁-C₄ alkyl, C₁-C₆ alkoxy, C₂-C₆,        alkylcarbonyl, phenyl or benzyl wherein each of the phenyl or        the benzyl may be optionally substituted with 1-3 R⁵; or with a        5- or 6-membered saturated or unsaturated ring system, or with a        5-6 fused ring system, or with a 6-6 fused ring system each        containing 1-3 heteroatoms wherein each ring may be optionally        substituted with 1-3 R⁵, biphenyl or naphthyl optionally        substituted with 1-3 R⁵;        alternatively R¹¹ and R¹² may be taken together to form a 5- or        6-membered saturated or unsaturated ring containing 1-3        heteroatoms wherein each ring may be optionally substituted with        1-3 R⁵;        R¹³ is H, C₁-C₄ alkyl, C₁-C₆ alkoxy, C₂-C₆, alkylcarbonyl,        phenyl or benzyl wherein each of the phenyl or the benzyl may be        optionally substituted with 1-3 R⁵; or with a 5- or 6-membered        saturated or unsaturated ring system, or with a 5-6 fused ring        system, or with a 6-6 fused ring system each containing 1-3        heteroatoms wherein each ring may be optionally substituted with        1-3 R⁵, biphenyl or naphthyl optionally substituted with 1-3 R⁵;        and        alternatively R¹² and R¹³ may be taken together to form a 5- or        6-membered saturated or unsaturated ring containing 1-3        heteroatoms wherein each ring may be optionally substituted with        1-3 R⁵.        R¹⁴ is phenyl or benzyl wherein each of the phenyl or the benzyl        may be optionally substituted with 1-3

Another embodiment of the present disclosure may include a fungicidalcomposition for the control or prevention of fungal attack comprisingthe compounds described below and a phytologically acceptable carriermaterial.

Yet another embodiment of the present disclosure may include a methodfor the control or prevention of fungal attack on a plant, the methodincluding the steps of applying a fungicidally effective amount of oneor more of the compounds described below to at least one of the fungus,the plant, an area adjacent to the plant, and the seed adapted toproduce the plant.

The term “alkyl” refers to a branched, unbranched, or cyclic carbonchain, including methyl, ethyl, propyl, butyl, isopropyl, isobutyl,tertiary butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl and the like.

The term “alkenyl” refers to a branched, unbranched or cyclic carbonchain containing one or more double bonds including ethenyl, propenyl,butenyl, isopropenyl, isobutenyl, cyclohexenyl, and the like.

The term “alkynyl” refers to a branched or unbranched carbon chaincontaining one or more triple bonds including propynyl, butynyl and thelike.

As used throughout this specification, the term ‘R’ refers to the groupconsisting of C₂₋₈ alkyl, C₃₋₈ alkenyl or C₃₋₈ alkynyl, unless statedotherwise.

The term “alkoxy” refers to an —OR substituent.

The term “alkoxycarbonyl” refers to a —C(O)—OR substituent.

The term “alkylcarbonyl” refers to a —C(O)—R substituent.

The term “alkyl sulfonyl” refers to an —SO₂—R substituent.

The term “haloalkylsulfonyl” refers to an —SO₂—R substituent where R isfully or partially substituted with Cl, F, I, or Br or any combinationthereof.

The term “alkylthio” refers to an —S—R substituent.

The term “haloalkylthio” refers to an alkylthio, which is substitutedwith Cl, F, I, or Br or any combination thereof.

The term “halothio” refers to a sulfur substituted with three or five Fsubstituents.

The term “alkylaminocarbonyl” refers to a —C(O)—N(H)—R substituent.

The term “dialkylaminocarbonyl” refers to a —C(O)—NR₂ substituent.

The term “alkylcycloalkylamino” refers to a cycloalkylamino substituentthat is substituted with an alkyl group.

The term “trialkylsilyl” refers to —SiR₃.

The term “cyano” refers to a —C≡N substituent.

The term “hydroxyl” refers to an —OH substituent.

The term “amino” refers to a —NH₂ substituent.

The term “alkylamino” refers to a —N(H)—R substituent.

The term “dialkylamino” refers to a —NR₂ substituent.

The term “trialkylsilylalkyl” refers to a —SiR₃ substituent on an alkyl.

The term “alkoxyalkoxy” refers to —O(CH₂)_(n)O(CH₂)_(m)CH₃ where n is aninteger from 1-3 and m is 0-2.

The term “alkoxyalkyl” refers to an alkoxy substitution on an alkyl.

The term “haloalkoxyalkyl” refers to an alkoxy substitution on an alkylwhich is fully or partially substituted with Cl, F, Br, or I, or anycombination thereof.

The term “hydroxyalkyl” refers to an alkyl which is substituted with ahydroxyl group.

The term “haloalkoxy” refers to an —OR—X substituent, wherein X is Cl,F, Br, or I, or any combination thereof.

The term “haloalkyl” refers to an alkyl, which is substituted with Cl,F, I, or Br or any combination thereof.

The term “haloalkenyl” refers to an alkenyl, which is substituted withCl, F, 1, or Br or any combination thereof.

The term “haloalkynyl” refers to an alkynyl which is substituted withCl, F, I, or Br or any combination thereof.

The term “halogen” or “halo” refers to one or more halogen atoms,defined as F, Cl, Br, and I.

The term “hydroxycarbonyl” refers to a —C(O)—OH substituent.

The term “nitro” refers to a —NO₂ substituent.

Throughout the disclosure, reference to the compounds of Formula I isread as also including optical isomers and salts of Formula I, andhydrates thereof. Specifically, when Formula I contains a branched chainalkyl group, it is understood that such compounds include opticalisomers and racemates thereof. Exemplary salts include: hydrochloride,hydrobromide, hydroiodide, and the like. Additionally, the compounds ofFormula I may include tautomeric forms.

Certain compounds disclosed in this document can exist as one or moreisomers. It will be appreciated by those skilled in the art that oneisomer may be more active than the others. The structures disclosed inthe present disclosure are drawn in only one geometric form for clarity,but are intended to represent all geometric and tautomeric forms of themolecule.

It is also understood by those skilled in the art that additionalsubstitution is allowable, unless otherwise noted, as long as the rulesof chemical bonding and strain energy are satisfied and the productstill exhibits fungicidal activity.

Another embodiment of the present disclosure is a use of a compound ofFormula I, for protection of a plant against attack by a phytopathogenicorganism or the treatment of a plant infested by a phytopathogenicorganism, comprising the application of a compound of Formula I, or acomposition comprising the compound to soil, a plant, a part of a plant,foliage, and/or seeds.

Additionally, another embodiment of the present disclosure is acomposition useful for protecting a plant against attack by aphytopathogenic organism and/or treatment of a plant infested by aphytopathogenic organism comprising a compound of Formula I and aphytologically acceptable carrier material.

Additional features and advantages of the present invention will becomeapparent to those skilled in the art upon consideration of the followingdetailed description of the illustrative embodiments exemplifying thebest mode of carrying out the invention as presently perceived.

DETAILED DESCRIPTION OF THE DISCLOSURE

The compounds of the present disclosure may be applied by any of avariety of known techniques, either as the compounds or as formulationscomprising the compounds. For example, the compounds may be applied tothe roots, seeds or foliage of plants for the control of various fungi,without damaging the commercial value of the plants. The materials maybe applied in the form of any of the generally used formulation types,for example, as solutions, dusts, wettable powders, flowableconcentrates, or emulsifiable concentrates.

Preferably, the compounds of the present disclosure are applied in theform of a formulation, comprising one or more of the compounds ofFormula I with a phytologically acceptable carrier. Concentratedformulations may be dispersed in water, or other liquids, forapplication, or formulations may be dust-like or granular, which maythen be applied without further treatment. The formulations can beprepared according to procedures that are conventional in theagricultural chemical art.

The present disclosure contemplates all vehicles by which one or more ofthe compounds may be formulated for delivery and use as a fungicide.Typically, formulations are applied as aqueous suspensions or emulsions.Such suspensions or emulsions may be produced from water-soluble, watersuspendible, or emulsifiable formulations which are solids, usuallyknown as wettable powders; or liquids, usually known as emulsifiableconcentrates, aqueous suspensions, or suspension concentrates. As willbe readily appreciated, any material to which these compounds may beadded may be used, provided it yields the desired utility withoutsignificant interference with the activity of these compounds asantifungal agents.

Wettable powders, which may be compacted to form water dispersiblegranules, comprise an intimate mixture of one or more of the compoundsof Formula I, an inert carrier and surfactants. The concentration of thecompound in the wettable powder may be from about 10 percent to about 90percent by weight based on the total weight of the wettable powder, morepreferably about 25 weight percent to about 75 weight percent. In thepreparation of wettable powder formulations, the compounds may becompounded with any finely divided solid, such as prophyllite, talc,chalk, gypsum, Fuller's earth, bentonite, attapulgite, starch, casein,gluten, montmorillonite clays, diatomaceous earths, purified silicatesor the like. In such operations, the finely divided carrier andsurfactants are typically blended with the compound(s) and milled.

Emulsifiable concentrates of the compounds of Formula I may comprise aconvenient concentration, such as from about 10 weight percent to about50 weight percent of the compound, in a suitable liquid, based on thetotal weight of the concentrate. The compounds may be dissolved in aninert carrier, which is either a water-miscible solvent or a mixture ofwater-immiscible organic solvents, and emulsifiers. The concentrates maybe diluted with water and oil to form spray mixtures in the form ofoil-in-water emulsions. Useful organic solvents include aromatics,especially the high-boiling naphthalenic and olefinic portions ofpetroleum such as heavy aromatic naphtha. Other organic solvents mayalso be used, for example, terpenic solvents, including rosinderivatives, aliphatic ketones, such as cyclohexanone, and complexalcohols, such as 2-ethoxyethanol.

Emulsifiers which may be advantageously employed herein may be readilydetermined by those skilled in the art and include various nonionic,anionic, cationic and amphoteric emulsifiers, or a blend of two or moreemulsifiers. Examples of nonionic emulsifiers useful in preparing theemulsifiable concentrates include the polyalkylene glycol ethers andcondensation products of alkyl and aryl phenols, aliphatic alcohols,aliphatic amines or fatty acids with ethylene oxide, propylene oxidessuch as the ethoxylated alkyl phenols and carboxylic esters solubilizedwith the polyol or polyoxyalkylene. Cationic emulsifiers includequaternary ammonium compounds and fatty amine salts. Anionic emulsifiersinclude the oil-soluble salts (e.g., calcium) of alkylaryl sulfonicacids, oil-soluble salts or sulfated polyglycol ethers and appropriatesalts of phosphated polyglycol ether.

Representative organic liquids which may be employed in preparing theemulsifiable concentrates of the compounds of the present invention arethe aromatic liquids such as xylene, propyl benzene fractions; or mixednaphthalene fractions, mineral oils, substituted aromatic organicliquids such as dioctyl phthalate; kerosene; dialkyl amides of variousfatty acids, particularly the dimethyl amides of fatty glycols andglycol derivatives such as the n-butyl ether, ethyl ether or methylether of diethylene glycol, and the methyl ether of triethylene glycoland the like. Mixtures of two or more organic liquids may also beemployed in the preparation of the emulsifiable concentrate. Organicliquids include xylene, and propyl benzene fractions, with xylene beingmost preferred in some cases. Surface-active dispersing agents aretypically employed in liquid formulations and in an amount of from 0.1to 20 percent by weight based on the combined weight of the dispersingagent with one or more of the compounds. The formulations can alsocontain other compatible additives, for example, plant growth regulatorsand other biologically active compounds used in agriculture.

Aqueous suspensions comprise suspensions of one or more water-insolublecompounds of Formula I, dispersed in an aqueous vehicle at aconcentration in the range from about 5 to about 50 weight percent,based on the total weight of the aqueous suspension. Suspensions areprepared by finely grinding one or more of the compounds, and vigorouslymixing the ground material into a vehicle comprised of water andsurfactants chosen from the same types discussed above. Othercomponents, such as inorganic salts and synthetic or natural gums, mayalso be added to increase the density and viscosity of the aqueousvehicle. It is often most effective to grind and mix at the same time bypreparing the aqueous mixture and homogenizing it in an implement suchas a sand mill, ball mill, or piston-type homogenizer.

Aqueous emulsions comprise emulsions of one or more water-insolublepesticidally active ingredients emulsified in an aqueous vehicle at aconcentration typically in the range from about 5 to about 50 weightpercent, based on the total weight of the aqueous emulsion. If thepesticidally active ingredient is a solid it must be dissolved in asuitable water-immiscible solvent prior to the preparation of theaqueous emulsion. Emulsions are prepared by emulsifying the liquidpesticidally active ingredient or water-immiscible solution thereof intoan aqueous medium typically with inclusion of surfactants that aid inthe formation and stabilization of the emulsion as described above. Thisis often accomplished with the aid of vigorous mixing provided by highshear mixers or homogenizers.

The compounds of Formula I can also be applied as granular formulations,which are particularly useful for applications to the soil. Granularformulations generally contain from about 0.5 to about 10 weightpercent, based on the total weight of the granular formulation of thecompound(s), dispersed in an inert carrier which consists entirely or inlarge part of coarsely divided inert material such as attapulgite,bentonite, diatomite, clay or a similar inexpensive substance. Suchformulations are usually prepared by dissolving the compounds in asuitable solvent and applying it to a granular carrier which has beenpreformed to the appropriate particle size, in the range of from about0.5 to about 3 mm. A suitable solvent is a solvent in which the compoundis substantially or completely soluble. Such formulations may also beprepared by making a dough or paste of the carrier and the compound andsolvent, and crushing and drying to obtain the desired granularparticle.

Dusts containing the compounds of Formula I may be prepared byintimately mixing one or more of the compounds in powdered form with asuitable dusty agricultural carrier, such as, for example, kaolin clay,ground volcanic rock, and the like. Dusts can suitably contain fromabout 1 to about 10 weight percent of the compounds, based on the totalweight of the dust.

The formulations may additionally contain adjuvant surfactants toenhance deposition, wetting and penetration of the compounds onto thetarget crop and organism. These adjuvant surfactants may optionally beemployed as a component of the formulation or as a tank mix. The amountof adjuvant surfactant will typically vary from 0.01 to 1.0 percent byvolume, based on a spray-volume of water, preferably 0.05 to 0.5 volumepercent. Suitable adjuvant surfactants include, but are not limited toethoxylated nonyl phenols, ethoxylated synthetic or natural alcohols,salts of the esters or sulfosuccinic acids, ethoxylated organosilicones,ethoxylated fatty amines and blends of surfactants with mineral orvegetable oils. The formulations may also include oil-in-water emulsionssuch as those disclosed in U.S. patent application Ser. No. 11/495,228,the disclosure of which is expressly incorporated by reference herein.

The formulations may optionally include combinations that contain otherpesticidal compounds. Such additional pesticidal compounds may befungicides, insecticides, herbicides, nematocides, miticides,arthropodicides, bactericides or combinations thereof that arecompatible with the compounds of the present invention in the mediumselected for application, and not antagonistic to the activity of thepresent compounds. Accordingly, in such embodiments, the otherpesticidal compound is employed as a supplemental toxicant for the sameor for a different pesticidal use. The compounds of Formula I and thepesticidal compound in the combination can generally be present in aweight ratio of from 1:100 to 100:1.

The compounds of the present disclosure may also be combined with otherfungicides to form fungicidal mixtures and synergistic mixtures thereof.The fungicidal compounds of the present disclosure are often applied inconjunction with one or more other fungicides to control a wider varietyof undesirable diseases. When used in conjunction with otherfungicide(s), the presently claimed compounds may be formulated with theother fungicide(s), tank mixed with the other fungicide(s) or appliedsequentially with the other fungicide(s). Such other fungicides mayinclude 2-(thiocyanatomethylthio)-benzothiazole, 2-phenylphenol,8-hydroxyquinoline sulfate, ametoctradin, amisulbrom, antimycin,Ampelomyces quisqualis, azaconazole, azoxystrobin, Bacillus subtilis,Bacillus subtilis strain QST713, benalaxyl, benomyl,benthiavalicarb-isopropyl, benzylaminobenzene-sulfonate (BABS) salt,bicarbonates, biphenyl, bismerthiazol, bitertanol, bixafen,blasticidin-S, borax, Bordeaux mixture, boscalid, bromuconazole,bupirimate, calcium polysulfide, captafol, captan, carbendazim,carboxin, carpropamid, carvone, chlazafenone, chloroneb, chlorothalonil,chlozolinate, Coniothyrium minitans, copper hydroxide, copper octanoate,copper oxychloride, copper sulfate, copper sulfate (tribasic), cuprousoxide, cyazofamid, cyflufenamid, cymoxanil, cyproconazole, cyprodinil,dazomet, debacarb, diammonium ethylenebis-(dithiocarbamate),dichlofluanid, dichlorophen, diclocymet, diclomezine, dichloran,diethofencarb, difenoconazole, difenzoquat ion, diflumetorim,dimethomorph, dimoxystrobin, diniconazole, diniconazole-M, dinobuton,dinocap, diphenylamine, dithianon, dodemorph, dodemorph acetate, dodine,dodine free base, edifenphos, enestrobin, epoxiconazole, ethaboxam,ethoxyquin, etridiazole, famoxadone, fenamidone, fenarimol,fenbuconazole, fenfuram, fenhexamid, fenoxanil, fenpiclonil,fenpropidin, fenpropimorph, fenpyrazamine, fentin, fentin acetate,fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, flumorph,fluopicolide, fluopyram, fluoroimide, fluoxastrobin, fluquinconazole,flusilazole, flusulfamide, flutianil, flutolanil, flutriafol,fluxapyroxad, folpet, formaldehyde, fosetyl, fosetyl-aluminium,fuberidazole, furalaxyl, furametpyr, guazatine, guazatine acetates,GY-81, hexachlorobenzene, hexaconazole, hymexazol, imazalil, imazalilsulfate, imibenconazole, iminoctadine, iminoctadine triacetate,iminoctadine tris(albesilate), iodocarb, ipconazole, ipfenpyrazolone,iprobenfos, iprodione, iprovalicarb, isoprothiolane, isopyrazam,isotianil, kasugamycin, kasugamycin hydrochloride hydrate,kresoxim-methyl, laminarin, mancopper, mancozeb, mandipropamid, maneb,mepanipyrim, mepronil, meptyl-dinocap, mercuric chloride, mercuricoxide, mercurous chloride, metalaxyl, mefenoxam, metalaxyl-M, metam,metam-ammonium, metam-potassium, metam-sodium, metconazole,methasulfocarb, methyl iodide, methyl isothiocyanate, metiram,metominostrobin, metrafenone, mildiomycin, myclobutanil, nabam,nitrothal-isopropyl, nuarimol, octhilinone, ofurace, oleic acid (fattyacids), orysastrobin, oxadixyl, oxine-copper, oxpoconazole fumarate,oxycarboxin, pefurazoate, penconazole, pencycuron, penflufen,pentachlorophenol, pentachlorophenyl laurate, penthiopyrad,phenylmercury acetate, phosphonic acid, phthalide, picoxystrobin,polyoxin B, polyoxins, polyoxorim, potassium bicarbonate, potassiumhydroxyquinoline sulfate, probenazole, prochloraz, procymidone,propamocarb, propamocarb hydrochloride, propiconazole, propineb,proquinazid, prothioconazole, pyraclostrobin, pyrametostrobin,pyraoxystrobin, pyrazophos, pyribencarb, pyributicarb, pyrifenox,pyrimethanil, pyriofenone, pyroquilon, quinoclamine, quinoxyfen,quintozene, Reynoutria sachalinensis extract, sedaxane, silthiofam,simeconazole, sodium 2-phenylphenoxide, sodium bicarbonate, sodiumpentachlorophenoxide, spiroxamine, sulfur, SYP-Z071, SYP-Z048, tar oils,tebuconazole, tebufloquin, tecnazene, tetraconazole, thiabendazole,thifluzamide, thiophanate-methyl, thiram, tiadinil, tolclofos-methyl,tolylfluanid, triadimefon, triadimenol, triazoxide, tricyclazole,tridemorph, trifloxystrobin, triflumizole, triforine, triticonazole,validamycin, valifenalate, valiphenal, vinclozolin, zineb, ziram,zoxamide, Candida oleophila, Fusarium oxysporum, Gliocladium spp.,Phlebiopsis gigantea, Streptomyces griseoviridis, Trichoderma spp.,(RS)—N-(3,5-dichlorophenyl)-2-(methoxymethyl)-succinimide,1,2-dichloropropane, 1,3-dichloro-1,1,3,3-tetrafluoroacetone hydrate,1-chloro-2,4-dinitronaphthalene, 1-chloro-2-nitropropane,2-(2-heptadecyl-2-imidazolin-1-yl)ethanol,2,3-dihydro-5-phenyl-1,4-dithi-ine 1,1,4,4-tetraoxide,2-methoxyethylmercury acetate, 2-methoxyethylmercury chloride,2-methoxyethylmercury silicate, 3-(4-chlorophenyl)-5-methylrhodanine,4-(2-nitroprop-1-enyl)phenyl thiocyanateme, ampropylfos, anilazine,azithiram, barium polysulfide, Bayer 32394, benodanil, benquinox,bentaluron, benzamacril; benzamacril-isobutyl, benzamorf, binapacryl,bis(methylmercury) sulfate, bis(tributyltin) oxide, buthiobate, cadmiumcalcium copper zinc chromate sulfate, carbamorph, CECA, chlobenthiazone,chloraniformethan, chlorfenazole, chlorquinox, climbazole, cyclafuramid,cypendazole, cyprofuram, decafentin, dichlone, dichlozoline,diclobutrazol, dimethirimol, dinocton, dinosulfon, dinoterbon,dipyrithione, ditalimfos, dodicin, drazoxolon, EBP, ESBP, etaconazole,etem, ethirim, fenaminosulf, fenapanil, fenitropan, 5-fluorocytosine andprofungicides thereof, fluotrimazole, furcarbanil, furconazole,furconazole-cis, furmecyclox, furophanate, glyodine, griseofulvin,halacrinate, Hercules 3944, hexylthiofos, ICIA0858, isopamphos,isovaledione, mebenil, mecarbinzid, metazoxolon, methfuroxam,methylmercury dicyandiamide, metsulfovax, milneb, mucochloric anhydride,myclozolin, N-3,5-dichlorophenyl-succinimide,N-3-nitrophenylitaconimide, natamycin,N-ethylmercurio-4-toluenesulfonanilide, nickelbis(dimethyldithiocarbamate), OCH, phenylmercurydimethyldithiocarbamate, phenylmercury nitrate, phosdiphen, picolinamideUK-2A and derivatives thereof, prothiocarb; prothiocarb hydrochloride,pyracarbolid, pyridinitril, pyroxychlor, pyroxyfur, quinacetol;quinacetol sulfate, quinazamid, quinconazole, rabenzazole,salicylanilide, SSF-109, sultropen, tecoram, thiadifluor, thicyofen,thiochlorfenphim, thiophanate, thioquinox, tioxymid, triamiphos,triarimol, triazbutil, trichlamide, urbacid, zarilamide, and anycombinations thereof.

Additionally, the compounds of the present invention may be combinedwith other pesticides, including insecticides, nematocides, miticides,arthropodicides, bactericides or combinations thereof that arecompatible with the compounds of the present invention in the mediumselected for application, and not antagonistic to the activity of thepresent compounds to form pesticidal mixtures and synergistic mixturesthereof. The fungicidal compounds of the present disclosure may beapplied in conjunction with one or more other pesticides to control awider variety of undesirable pests. When used in conjunction with otherpesticides, the presently claimed compounds may be formulated with theother pesticide(s), tank mixed with the other pesticide(s) or appliedsequentially with the other pesticide(s). Typical insecticides include,but are not limited to: antibiotic insecticides such as allosamidin andthuringiensin; macrocyclic lactone insecticides such as spinosad andspinetoram; avermectin insecticides such as abamectin, doramectin,emamectin, eprinomectin, ivermectin and selamectin; milbemycininsecticides such as lepimectin, milbemectin, milbemycin oxime andmoxidectin; arsenical insecticides such as calcium arsenate, copperacetoarsenite, copper arsenate, lead arsenate, potassium arsenite andsodium arsenite; botanical insecticides such as anabasine, azadirachtin,d-limonene, nicotine, pyrethrins, cinerins, cinerin I, cinerin II,jasmolin I, jasmolin II, pyrethrin I, pyrethrin II, quassia, rotenone,ryania and sabadilla; carbamate insecticides such as bendiocarb andcarbaryl; benzofuranyl methylcarbamate insecticides such as benfuracarb,carbofuran, carbosulfan, decarbofuran and furathiocarb;dimethylcarbamate insecticides dimitan, dimetilan, hyquincarb andpirimicarb; oxime carbamate insecticides such as alanycarb, aldicarb,aldoxycarb, butocarboxim, butoxycarboxim, methomyl, nitrilacarb, oxamyl,tazimcarb, thiocarboxime, thiodicarb and thiofanox; phenylmethylcarbamate insecticides such as allyxycarb, aminocarb, bufencarb,butacarb, carbanolate, cloethocarb, dicresyl, dioxacarb, EMPC,ethiofencarb, fenethacarb, fenobucarb, isoprocarb, methiocarb,metolcarb, mexacarbate, promacyl, promecarb, propoxur, trimethacarb, XMCand xylylcarb; dessicans insecticides such as boric acid, diatomaceousearth and silica gel; diamide insecticides such as chlorantraniliprole,cyantraniliprole and flubendiamide; dinitrophenol insecticides such asdinex, dinoprop, dinosam and DNOC; fluorine insecticides such as bariumhexafluorosilicate, cryolite, sodium fluoride, sodium hexafluorosilicateand sulfluramid; formamidine insecticides such as amitraz,chlordimeform, formetanate and formparanate; fumigant insecticides suchas acrylonitrile, carbon disulfide, carbon tetrachloride, chloroform,chloropicrin, para-dichlorobenzene, 1,2-dichloropropane, ethyl formate,ethylene dibromide, ethylene dichloride, ethylene oxide, hydrogencyanide, iodomethane, methyl bromide, methylchloroform, methylenechloride, naphthalene, phosphine, sulfuryl fluoride andtetrachloroethane; inorganic insecticides such as borax, calciumpolysulfide, copper oleate, mercurous chloride, potassium thiocyanateand sodium thiocyanate; chitin synthesis inhibitors such asbistrifluoron, buprofezin, chlorfluazuron, cyromazine, diflubenzuron,flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron,noviflumuron, penfluoron, teflubenzuron and triflumuron; juvenilehormone mimics such as epofenonane, fenoxycarb, hydroprene, kinoprene,methoprene, pyriproxyfen and triprene; juvenile hormones such asjuvenile hormone I, juvenile hormone II and juvenile hormone III;moulting hormone agonists such as chromafenozide, halofenozide,methoxyfenozide and tebufenozide; moulting hormones such as α-ecdysoneand ecdysterone; moulting inhibitors such as diofenolan; precocenes suchas precocene I, precocene II and precocene III; unclassified insectgrowth regulators such as dicyclanil; nereistoxin analogue insecticidessuch as bensultap, cartap, thiocyclam and thiosultap; nicotinoidinsecticides such as flonicamid; nitroguanidine insecticides such asclothianidin, dinotefuran, imidacloprid and thiamethoxam; nitromethyleneinsecticides such as nitenpyram and nithiazine; pyridylmethyl-amineinsecticides such as acetamiprid, imidacloprid, nitenpyram andthiacloprid; organochlorine insecticides such as bromo-DDT, camphechlor,DDT, pp′-DDT, ethyl-DDD, HCH, gamma-HCH, lindane, methoxychlor,pentachlorophenol and TDE; cyclodiene insecticides such as aldrin,bromocyclen, chlorbicyclen, chlordane, chlordecone, dieldrin, dilor,endosulfan, alpha-endosulfan, endrin, HEOD, heptachlor, HHDN, isobenzan,isodrin, kelevan and mirex; organophosphate insecticides such asbromfenvinfos, chlorfenvinphos, crotoxyphos, dichlorvos, dicrotophos,dimethylvinphos, fospirate, heptenophos, methocrotophos, mevinphos,monocrotophos, naled, naftalofos, phosphamidon, propaphos, TEPP andtetrachlorvinphos; organothiophosphate insecticides such asdioxabenzofos, fosmethilan and phenthoate; aliphatic organothiophosphateinsecticides such as acethion, amiton, cadusafos, chlorethoxyfos,chlormephos, demephion, demephion-O, demephion-S, demeton, demeton-O,demeton-S, demeton-methyl, demeton-O-methyl, demeton-S-methyl,demeton-S-methylsulphon, disulfoton, ethion, ethoprophos, IPSP,isothioate, malathion, methacrifos, oxydemeton-methyl, oxydeprofos,oxydisulfoton, phorate, sulfotep, terbufos and thiometon; aliphaticamide organothiophosphate insecticides such as amidithion, cyanthoate,dimethoate, ethoate-methyl, formothion, mecarbam, omethoate, prothoate,sophamide and vamidothion; oxime organothiophosphate insecticides suchas chlorphoxim, phoxim and phoxim-methyl; heterocyclicorganothiophosphate insecticides such as azamethiphos, coumaphos,coumithoate, dioxathion, endothion, menazon, morphothion, phosalone,pyraclofos, pyridaphenthion and quinothion; benzothiopyranorganothiophosphate insecticides such as dithicrofos and thicrofos;benzotriazine organothiophosphate insecticides such as azinphos-ethyland azinphos-methyl; isoindole organothiophosphate insecticides such asdialifos and phosmet; isoxazole organothiophosphate insecticides such asisoxathion and zolaprofos; pyrazolopyrimidine organothiophosphateinsecticides such as chlorprazophos and pyrazophos; pyridineorganothiophosphate insecticides such as chlorpyrifos andchlorpyrifos-methyl; pyrimidine organothiophosphate insecticides such asbutathiofos, diazinon, etrimfos, lirimfos, pirimiphos-ethyl,pirimiphos-methyl, primidophos, pyrimitate and tebupirimfos; quinoxalineorganothiophosphate insecticides such as quinalphos andquinalphos-methyl; thiadiazole organothiophosphate insecticides such asathidathion, lythidathion, methidathion and prothidathion; triazoleorganothiophosphate insecticides such as isazofos and triazophos; phenylorganothiophosphate insecticides such as azothoate, bromophos,bromophos-ethyl, carbophenothion, chlorthiophos, cyanophos, cythioate,dicapthon, dichlofenthion, etaphos, famphur, fenchlorphos, fenitrothionfensulfothion, fenthion, fenthion-ethyl, heterophos, jodfenphos,mesulfenfos, parathion, parathion-methyl, phenkapton, phosnichlor,profenofos, prothiofos, sulprofos, temephos, trichlormetaphos-3 andtrifenofos; phosphonate insecticides such as butonate and trichlorfon;phosphonothioate insecticides such as mecarphon; phenylethylphosphonothioate insecticides such as fonofos and trichloronat;phenyl phenylphosphonothioate insecticides such as cyanofenphos, EPN andleptophos; phosphoramidate insecticides such as crufomate, fenamiphos,fosthietan, mephosfolan, phosfolan and pirimetaphos;phosphoramidothioate insecticides such as acephate, isocarbophos,isofenphos, isofenphos-methyl, methamidophos and propetamphos;phosphorodiamide insecticides such as dimefox, mazidox, mipafox andschradan; oxadiazine insecticides such as indoxacarb; oxadiazolineinsecticides such as metoxadiazone; phthalimide insecticides such asdialifos, phosmet and tetramethrin; pyrazole insecticides such astebufenpyrad, tolefenpyrad; phenylpyrazole insecticides such asacetoprole, ethiprole, fipronil, pyrafluprole, pyriprole andvaniliprole; pyrethroid ester insecticides such as acrinathrin,allethrin, bioallethrin, barthrin, bifenthrin, bioethanomethrin,cyclethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin,gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin,beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin,deltamethrin, dimefluthrin, dimethrin, empenthrin, fenfluthrin,fenpirithrin, fenpropathrin, fenvalerate, esfenvalerate, flucythrinate,fluvalinate, tau-fluvalinate, furethrin, imiprothrin, meperfluthrin,metofluthrin, permethrin, biopermethrin, transpermethrin, phenothrin,prallethrin, profluthrin, pyresmethrin, resmethrin, bioresmethrin,cismethrin, tefluthrin, terallethrin, tetramethrin, tetramethylfluthrin,tralomethrin and transfluthrin; pyrethroid ether insecticides such asetofenprox, flufenprox, halfenprox, protrifenbute and silafluofen;pyrimidinamine insecticides such as flufenerim and pyrimidifen; pyrroleinsecticides such as chlorfenapyr; tetramic acid insecticides such asspirotetramat; tetronic acid insecticides such as spiromesifen; thioureainsecticides such as diafenthiuron; urea insecticides such as flucofuronand sulcofuron; and unclassified insecticides such as closantel, coppernaphthenate, crotamiton, EXD, fenazaflor, fenoxacrim, hydramethylnon,isoprothiolane, malonoben, metaflumizone, nifluridide, plifenate,pyridaben, pyridalyl, pyrifluquinazon, rafoxanide, sulfoxaflor,triarathene and triazamate, and any combinations thereof.

Additionally, the compounds of the present invention may be combinedwith herbicides that are compatible with the compounds of the presentinvention in the medium selected for application, and not antagonisticto the activity of the present compounds to form pesticidal mixtures andsynergistic mixtures thereof. The fungicidal compounds of the presentdisclosure may be applied in conjunction with one or more herbicides tocontrol a wide variety of undesirable plants. When used in conjunctionwith herbicides, the presently claimed compounds may be formulated withthe herbicide(s), tank mixed with the herbicide(s) or appliedsequentially with the herbicide(s). Typical herbicides include, but arenot limited to: amide herbicides such as allidochlor, beflubutamid,benzadox, benzipram, bromobutide, cafenstrole, CDEA, cyprazole,dimethenamid, dimethenamid-P, diphenamid, epronaz, etnipromid,fentrazamide, flupoxam, fomesafen, halosafen, isocarbamid, isoxaben,napropamide, naptalam, pethoxamid, propyzamide, quinonamid and tebutam;anilide herbicides such as chloranocryl, cisanilide, clomeprop,cypromid, diflufenican, etobenzanid, fenasulam, flufenacet, flufenican,mefenacet, mefluidide, metamifop, monalide, naproanilide, pentanochlor,picolinafen and propanil; arylalanine herbicides such as benzoylprop,flampropand flamprop-M; chloroacetanilide herbicides such as acetochlor,alachlor, butachlor, butenachlor, delachlor, diethatyl, dimethachlor,metazachlor, metolachlor, S-metolachlor, pretilachlor, propachlor,propisochlor, prynachlor, terbuchlor, thenylchlor and xylachlor;sulfonanilide herbicides such as benzofluor, perfluidone, pyrimisulfanand profluazol; sulfonamide herbicides such as asulam, carbasulam,fenasulam and oryzalin; thioamide herbicides such as chlorthiamid;antibiotic herbicides such as bilanafos; benzoic acid herbicides such aschloramben, dicamba, 2,3,6-TBA and tricamba; pyrimidinyloxybenzoic acidherbicides such as bispyribac and pyriminobac; pyrimidinylthiobenzoicacid herbicides such as pyrithiobac; phthalic acid herbicides such aschlorthal; picolinic acid herbicides such as aminopyralid, clopyralidand picloram; quinolinecarboxylic acid herbicides such as quinclorac andquinmerac; arsenical herbicides such as cacodylic acid, CMA, DSMA,hexaflurate, MAA, MAMA, MSMA, potassium arsenite and sodium arsenite;benzoylcyclohexanedione herbicides such as mesotrione, sulcotrione,tefuryltrione and tembotrione; benzofuranyl alkylsulfonate herbicidessuch as benfuresate and ethofumesate; benzothiazole herbicides such asbenzazolin; carbamate herbicides such as asulam, carboxazolechlorprocarb, dichlormate, fenasulam, karbutilate and terbucarb;carbanilate herbicides such as barban, BCPC, carbasulam, carbetamide,CEPC, chlorbufam, chlorpropham, CPPC, desmedipham, phenisopham,phenmedipham, phenmedipham-ethyl, propham and swep; cyclohexene oximeherbicides such as alloxydim, butroxydim, clethodim, cloproxydim,cycloxydim, profoxydim, sethoxydim, tepraloxydim and tralkoxydim;cyclopropylisoxazole herbicides such as isoxachlortole and isoxaflutole;dicarboximide herbicides such as cinidon-ethyl, flumezin, flumiclorac,flumioxazin and flumipropyn; dinitroaniline herbicides such asbenfluralin, butralin, dinitramine, ethalfluralin, fluchloralin,isopropalin, methalpropalin, nitralin, oryzalin, pendimethalin,prodiamine, profluralin and trifluralin; dinitrophenol herbicides suchas dinofenate, dinoprop, dinosam, dinoseb, dinoterb, DNOC, etinofen andmedinoterb; diphenyl ether herbicides such as ethoxyfen; nitrophenylether herbicides such as acifluorfen, aclonifen, bifenox,chlomethoxyfen, chlornitrofen, etnipromid, fluorodifen, fluoroglycofen,fluoronitrofen, fomesafen, furyloxyfen, halosafen, lactofen, nitrofen,nitrofluorfen and oxyfluorfen; dithiocarbamate herbicides such asdazomet and metam; halogenated aliphatic herbicides such as alorac,chloropon, dalapon, flupropanate, hexachloroacetone, iodomethane, methylbromide, monochloroacetic acid, SMA and TCA; imidazolinone herbicidessuch as imazamethabenz, imazamox, imazapic, imazapyr, imazaquin andimazethapyr; inorganic herbicides such as ammonium sulfamate, borax,calcium chlorate, copper sulfate, ferrous sulfate, potassium azide,potassium cyanate, sodium azide, sodium chlorate and sulfuric acid;nitrile herbicides such as bromobonil, bromoxynil, chloroxynil,dichlobenil, iodobonil, ioxynil and pyraclonil; organophosphorusherbicides such as amiprofos-methyl, anilofos, bensulide, bilanafos,butamifos, 2,4-DEP, DMPA, EBEP, fosamine, glufosinate, glufosinate-P,glyphosate and piperophos; phenoxy herbicides such as bromofenoxim,clomeprop, 2,4-DEB, 2,4-DEP, difenopenten, disul, erbon, etnipromid,fenteracol and trifopsime; oxadiazoline herbicides such as methazole,oxadiargyl, oxadiazon; oxazole herbicides such as fenoxasulfone;phenoxyacetic herbicides such as 4-CPA, 2,4-D, 3,4-DA, MCPA,MCPA-thioethyl and 2,4,5-T; phenoxybutyric herbicides such as 4-CPB,2,4-DB, 3,4-DB, MCPB and 2,4,5-TB; phenoxypropionic herbicides such ascloprop, 4-CPP, dichlorprop, dichlorprop-P, 3,4-DP, fenoprop,mecopropand mecoprop-P; aryloxyphenoxypropionic herbicides such aschlorazifop, clodinafop, clofop, cyhalofop, diclofop, fenoxaprop,fenoxaprop-P, fenthiaprop, fluazifop, fluazifop-P, haloxyfop,haloxyfop-P, isoxapyrifop, metamifop, propaquizafop, quizalofop,quizalofop-P and trifop; phenylenediamine herbicides such as dinitramineand prodiamine; pyrazole herbicides such as pyroxasulfone;benzoylpyrazole herbicides such as benzofenap, pyrasulfotole,pyrazolynate, pyrazoxyfen, and topramezone; phenylpyrazole herbicidessuch as fluazolate, nipyraclofen, pioxaden and pyraflufen; pyridazineherbicides such as credazine, pyridafol and pyridate; pyridazinoneherbicides such as brompyrazon, chloridazon, dimidazon, flufenpyr,metflurazon, norflurazon, oxapyrazon and pydanon; pyridine herbicidessuch as aminopyralid, cliodinate, clopyralid, dithiopyr, fluoroxypyr,haloxydine, picloram, picolinafen, pyriclor, thiazopyr and triclopyr;pyrimidinediamine herbicides such as iprymidam and tioclorim; quaternaryammonium herbicides such as cyperquat, diethamquat, difenzoquat, diquat,morfamquat and paraquat; thiocarbamate herbicides such as butylate,cycloate, di-allate, EPTC, esprocarb, ethiolate, isopolinate,methiobencarb, molinate, orbencarb, pebulate, pro sulfocarb,pyributicarb, sulfallate, thiobencarb, tiocarbazil, tri-allate andvernolate; thiocarbonate herbicides such as dimexano, EXD and proxan;thiourea herbicides such as methiuron; triazine herbicides such asdipropetryn, indaziflam, triaziflam and trihydroxytriazine;chlorotriazine herbicides such as atrazine, chlorazine, cyanazine,cyprazine, eglinazine, ipazine, mesoprazine, procyazine, proglinazine,propazine, sebuthylazine, simazine, terbuthylazine and trietazine;methoxytriazine herbicides such as atraton, methometon, prometon,secbumeton, simeton and terbumeton; methylthiotriazine herbicides suchas ametryn, aziprotryne, cyanatryn, desmetryn, dimethametryn,methoprotryne, prometryn, simetryn and terbutryn; triazinone herbicidessuch as ametridione, amibuzin, hexazinone, isomethiozin, metamitron andmetribuzin; triazole herbicides such as amitrole, cafenstrole, epronazand flupoxam; triazolone herbicides such as amicarbazone, bencarbazone,carfentrazone, flucarbazone, ipfencarbazone, propoxycarbazone,sulfentrazone and thiencarbazone-methyl; triazolopyrimidine herbicidessuch as cloransulam, diclosulam, florasulam, flumetsulam, metosulam,penoxsulam and pyroxsulam; uracil herbicides such as benzfendizone,bromacil, butafenacil, flupropacil, isocil, lenacil, saflufenacil andterbacil; urea herbicides such as benzthiazuron, cumyluron, cycluron,dichloralurea, diflufenzopyr, isonoruron, isouron, methabenzthiazuron,monisouron and noruron; phenylurea herbicides such as anisuron, buturon,chlorbromuron, chloreturon, chlorotoluron, chloroxuron, daimuron,difenoxuron, dimefuron, diuron, fenuron, fluometuron, fluothiuron,isoproturon, linuron, methiuron, methyldymron, metobenzuron,metobromuron, metoxuron, monolinuron, monuron, neburon, parafluoron,phenobenzuron, siduron, tetrafluoron and thidiazuron;pyrimidinylsulfonylurea herbicides such as amidosulfuron, azimsulfuron,bensulfuron, chlorimuron, cyclosulfamuron, ethoxysulfuron,flazasulfuron, flucetosulfuron, flupyrsulfuron, foramsulfuron,halosulfuron, imazosulfuron, mesosulfuron, metazosulfuron, nicosulfuron,orthosulfamuron, oxasulfuron, primisulfuron, propyrisulfuron,pyrazosulfuron, rimsulfuron, sulfometuron, sulfosulfuron andtrifloxysulfuron; triazinylsulfonylurea herbicides such aschlorsulfuron, cinosulfuron, ethametsulfuron, iodosulfuron, metsulfuron,prosulfuron, thifensulfuron, triasulfuron, tribenuron, triflusulfuronand tritosulfuron; thiadiazolylurea herbicides such as buthiuron,ethidimuron, tebuthiuron, thiazafluoron and thidiazuron; andunclassified herbicides such as acrolein, allyl alcohol,aminocyclopyrachlor, azafenidin, bentazone, benzobicyclon,bicyclopyrone, buthidazole, calcium cyanamide, cambendichlor,chlorfenac, chlorfenprop, chlorflurazole, chlorflurenol, cinmethylin,clomazone, CPMF, cresol, cyanamide, ortho-dichlorobenzene, dimepiperate,endothal, fluoromidine, fluridone, fluorochloridone, flurtamone,fluthiacet, indanofan, methyl isothiocyanate, OCH, oxaziclomefone,pentachlorophenol, pentoxazone, phenylmercury acetate, pro sulfalin,pyribenzoxim, pyriftalid, quinoclamine, rhodethanil, sulglycapin,thidiazimin, tridiphane, trimeturon, tripropindan and tritac.

Another embodiment of the present disclosure is a method for the controlor prevention of fungal attack. This method comprises applying to thesoil, plant, roots, foliage, seed or locus of the fungus, or to a locusin which the infestation is to be prevented (for example applying tocereal plants), a fungicidally effective amount of one or more of thecompounds of Formula I. The compounds are suitable for treatment ofvarious plants at fungicidal levels, while exhibiting low phytotoxicity.The compounds may be useful both in a protectant and/or an eradicantfashion.

The compounds have been found to have significant fungicidal effectparticularly for agricultural use. Many of the compounds areparticularly effective for use with agricultural crops and horticulturalplants. Additional benefits may include, but are not limited to,improving the health of a plant; improving the yield of a plant (e.g.increased biomass and/or increased content of valuable ingredients);improving the vigor of a plant (e.g. improved plant growth and/orgreener leaves); improving the quality of a plant (e.g. improved contentor composition of certain ingredients); and improving the tolerance toabiotic and/or biotic stress of the plant.

It will be understood by those in the art that the efficacy of thecompound for the foregoing fungi establishes the general utility of thecompounds as fungicides.

The compounds have broad ranges of activity against fungal pathogens.Exemplary pathogens may include, but are not limited to, wheat leafblotch (Septoria tritici, also known as Mycosphaerella graminicola),apple scab (Venturia inaequalis), and Cercospora leaf spots of sugarbeets (Cercospora beticola), leaf spots of peanut (Cercosporaarachidicola and Cercosporidium personatum) and other crops, and blacksigatoka of bananas (Mycosphaerella fujiensis). The exact amount of theactive material to be applied is dependent not only on the specificactive material being applied, but also on the particular actiondesired, the fungal species to be controlled, and the stage of growththereof, as well as the part of the plant or other product to becontacted with the compound. Thus, all the compounds, and formulationscontaining the same, may not be equally effective at similarconcentrations or against the same fungal species.

The compounds are effective in use with plants in a disease-inhibitingand phytologically acceptable amount. The term “disease-inhibiting andphytologically acceptable amount” refers to an amount of a compound thatkills or inhibits the plant disease for which control is desired, but isnot significantly toxic to the plant. This amount will generally be fromabout 0.1 to about 1000 ppm (parts per million), with 1 to 500 ppm beingpreferred. The exact amount of a compound required varies with thefungal disease to be controlled, the type of formulation employed, themethod of application, the particular plant species, climate conditions,and the like. A suitable application rate is typically in the range fromabout 0.10 to about 4 pounds/acre (about 0.01 to 0.45 grams per squaremeter, g/m²).

Any range or desired value given herein may be extended or alteredwithout losing the effects sought, as is apparent to the skilled personfor an understanding of the teachings herein.

The compounds of Formula I may be made using well-known chemicalprocedures. Intermediates not specifically mentioned in this disclosureare either commercially available, may be made by routes disclosed inthe chemical literature, or may be readily synthesized from commercialstarting materials utilizing standard procedures.

The following examples are presented to illustrate the various aspectsof the compounds of the present disclosure and should not be construedas limitations to the claims.

Example 1 Preparation of5-fluoro-1-morpholin-4-ylmethyl-4-[(morpholin-4-ylmethyl)amino]-1H-pyrimidin-2-one(1)

This material was prepared as described in Int. J. Pharm. 1987, 35,243-252. To a mixture of paraformaldehyde (240 milligrams (mg), 8millimoles (mmol) of monomer) in dichloromethane (CH₂Cl₂; 20 mL) in a 25milliliter (mL) screw-cap vial was added morpholine (697 mg, 8 mmol).The reaction mixture was agitated on an orbital shaker overnight at roomtemperature. 4-Amino-5-fluoropyrimidin-2-ol* (250 mg, 2 mmol) was added,and the resulting heterogeneous mixture was agitated at room temperaturefor 48 hours (h). The reaction mixture was evaporated to dryness and theresidue was treated with ether (Et₂O) to give a white solid, which wasfiltered and dried to give the title compound (381 mg, 65%): mp 156-158°C.; ¹H NMR (300 MHz, CDCl₃) δ 7.46 (d, J=2.5 Hz, 1H), 5.69 (br t, 1H),4.53 (s, 2H), 4.46 (d, J=2.6 Hz, 2H), 3.72 (m, 8H), 2.64 (m, 8H); IR(ATR) 3483 (br), 3293 (br), 1680 (s), 1639 (s), 1574 (s), 1521 (s) cm⁻¹.*4-Amino-5-fluoropyrimidin-2-ol can be purchased commercially.

Example 2 Preparation of5-fluoro-1-(4-methylpiperazin-1-ylmethyl)-4-[(4-methylpiperazin-1-ylmethyl)-amino]-1H-pyrimidin-2-one(2)

This material was prepared as described in Int. J. Pharm. 1987, 35,243-252. To a mixture of paraformaldehyde (240 mg, 8 mmol of monomer) inCH₂Cl₂ (20 mL) in a 25 mL screw-cap vial was added N-methylpiperazine(813 mg, 8 mmol). The reaction mixture was agitated on an orbital shakerovernight at room temperature. 4-Amino-5-fluoropyrimidin-2-ol (250 mg, 2mmol) was added and the resulting heterogeneous mixture was agitated atroom temperature for 48 h. The reaction mixture was evaporated todryness and the residue was treated with Et₂O to give a beige solid,which was filtered and dried to give the title compound (247 mg, 31%):mp 165-166° C.; ¹H NMR (300 MHz, CDCl₃) δ 7.45 (d, J=2.5 Hz, 1H), 5.62(br t, 1H), 4.55 (s, 2H), 4.5 (d, J=2.6 Hz, 2H), 2.69 (m, 8H), 2.44 (br,8H), 2.38 (s, 6H); IR (ATR) 3465 (br), 1679 (s), 1646 (s), 1574 (s),1522 (s) cm⁻¹.

Compound 3 in Table I was synthesized as in Example 2.

Example 3 Preparation ofN′-[5-fluoro-1-(4-fluorobenzyl)-2-oxo-1,2-dihydro-pyrimidin-4-yl]-N,N-dimethylformamidine(4)

To an 8 mL screw-cap vial was added N,N-dimethylformamide (DMF; 1.5 mL),N′-(5-fluoro-2-hydroxypyrimidin-4-yl)-N,N-dimethylformamidine (100 mg,0.54 mmol), anhydrous potassium carbonate (K₂CO₃; 138 mg, 1.0 mmol), and4-fluorobenzyl bromide (113 mg, 0.60 mmol). The mixture was shaken andheated to 70° C. for 2 h and then at room temperature for an additional16 h. The crude reaction mixture was filtered and placed directly onto areverse phase chromatography column. After elution, the title compoundwas isolated as a white solid (30 mg, 20%): mp 134-136° C.; ¹H NMR (300MHz, CDCl₃) δ 8.68 (s, 1H), 8.07 (d, J=2.5 Hz, 1H), 7.49-7.43 (m, 2H),7.10-7.01 (m, 2H), 5.33 (s, 2H), 3.20 (s, 3H), 3.18 (s, 3H); ESIMS m/z293 ([M+H]⁺).

Compounds 5-7 in Table I were synthesized as in Example 3.

Example 4 Preparation ofN-(5-fluoro-1-methyl-2-oxo-1,2-dihydro-pyrimidin-4-yl)-4-methyl-benzamide(8)

To N-(5-fluoro-2-hydroxypyrimidin-4-yl)-4-methylbenzamide (200 mg, 0.81mmol) in DMF (5 mL) was added K₂CO₃ (224 mg, 1.6 mmol), and iodomethane(230 mg, 1.6 mmol). The mixture was stirred and heated to 60° C. for 30min and then stirred for 16 h at room temperature. The mixture waspartitioned between ethyl acetate (EtOAc) and water (H₂O). The organicphase was dried over magnesium sulfate (MgSO₄), filtered and evaporated.The crude material was purified by reverse phase chromatography to yieldthe title compound as a white solid (17 mg, 8%): mp 229-230° C.; ¹H NMR(300 MHz, CDCl₃) δ 13.2 (br s, 1H), 8.23-8.15 (br m, 2H), 7.42-7.37 (brm, 1H), 7.30-7.25 (br m, 2H), 3.45 (s, 3H), 2.44 (s, 3H); ESIMS m/z 262([M+H]⁺), m/z 260 ([M−H]⁻).

Example 5 Preparation ofN-(5-fluoro-1-methyl-2-oxo-1,2-dihydropyrimidin-4-yl)-N-methyl-C-phenylmethanesulfonamide(9)

4-Amino-5-fluoropyrimidin-2-ol (2 grams (g), 15.5 mmol) was stirred inacetonitrile (CH₃CN; 80 mL) at 50° C. To the warm mixture was addedN,O-bis(trimethylsilyl)acetamide (BSA; 9.4 g, 46.3 mmol), and stirringand heating were continued for 1.5 h. Phenylmethanesulfonyl chloride(3.2 g, 16.8 mmol) was added. After 2 h, the reaction mixture was cooledto room temperature and partitioned between CH₃CN and brine. The organicphase was dried over MgSO₄, filtered, evaporated and placed directlyonto a silica gel column which was eluted (gradient, 0 to 100% EtOAc inpetroleum ether). Combining fractions containing the major UV absorbingportion of the product mixture yielded a white solid which was usedwithout further purification. To a portion of this material (100 mg) wasadded DMF (3 mL), K₂CO₃ (100 mg), and iodomethane (100 mg), and themixture was stirred at 60° C. for 1 h. The reaction mixture was cooledto room temperature and an excess of sodium hydride (NaH; 60% dispersionin mineral oil) was added. The whole mixture was stirred for 30 min andthen heated to 45° C. for 2.5 h. The crude mixture was filtered andpurified by reverse phase chromatography followed by normal phasechromatography (gradient, 30 to 100% EtOAc in petroleum ether) to yieldthe title compound as a white solid (28 mg, 27%): mp 159-160° C.; ¹H NMR(300 MHz, CDCl₃) δ 7.6 (m, 1H), 7.42-7.41 (m, 2H), 7.38-7.36 (m, 3H),4.8 (s, 2H), 3.5 (s, 3H), 2.82 (s, 3H); ESIMS ink 312 ([M+H]⁺), ink 310([M−H]⁻).

Example 6 Preparation of(5-fluoro-1-methyl-2-oxo-1,2-dihydropyrimidin-4-yl)carbamic acidisobutyl ester (10) and(5-fluoro-1-methyl-2-oxo-1,2-dihydropyrimidin-4-yl)methylcarbamic acidisobutyl ester (11)

4-Amino-5-fluoropyrimidin-2-ol (0.5 g, 3.9 mmol) and isobutylchloroformate (0.58 g, 4.2 mmol) were shaken in pyridine (5 mL) at 60°C. for 1.5 h. The crude mixture was partitioned between EtOAc and 1 Nhydrochloric acid (HCl). The organic phase was dried over MgSO₄,filtered and evaporated. The residue was precipitated from ethyl alcohol(EtOH) to furnish a white solid which was used without furtherpurification. A portion of this material (100 mg), K₂CO₃ (125 mg), andiodomethane (125 mg) were added to DMF (3 mL), and the mixture wasstirred at 60° C. for 1 h. The mixture was cooled to room temperatureand an excess of NaH (60% dispersion in mineral oil) was added. Theentire mixture was stirred for 30 min and then heated to 45° C. for 2 h.The crude mixture was filtered and purified by reverse phasechromatography to yield the title compounds.

(5-Fluoro-1-methyl-2-oxo-1,2-dihydropyrimidin-4-yl)carbamic acidisobutyl ester was isolated as a white solid (16 mg): mp 126-128° C.; ¹HNMR (300 MHz, CDCl₃) δ 12.2 (br s, 1H), 7.32 (br s, 1H), 3.98 (d, J=6.6Hz, 2H), 3.4 (s, 3H), 2.02 (sept, J=6.6 Hz, 1H), 1.01 (d, J=6.6 Hz, 6H);ESIMS m/z 244 (M+H⁺), m/z 242 ([M−H]⁻).

(5-Fluoro-1-methyl-2-oxo-1,2-dihydropyrimidin-4-yl)methylcarbamic acidisobutyl ester was isolated as a clear colorless oil (22 mg): ¹H NMR(300 MHz, CDCl₃) δ 7.52 (d, J=5.5 Hz, 1H), 4.02 (d, J=6.8 Hz, 2H), 3.55(s, 3H), 3.40 (s, 3H), 1.99 (sept, J=6.8 Hz, 1H), 0.95 (d, J=6.8 Hz,6H); ¹³C NMR (150 MHz, CDCl₃) δ 158.24, 158.17, 154.7, 154.1, 140.5,138.8, 134.0, 133.7, 73.6, 38.6, 34.9, 27.9, 19.2; ESIMS m/z 258([M+H]⁺).

Example 7 Preparation of 2,2-dimethylpropionic acid4-(dimethylamino-methyleneamino)-5-fluoro-2-oxo-2H-pyrimidin-1-ylmethylester (12)

To DMF (3 mL) were addedN′-(5-fluoro-2-hydroxypyrimidin-4-yl)-N,N-dimethylformamidine (100 mg,0.54 mmol), cesium carbonate (196 mg, 0.6 mmol), and chloromethylpivalate (90 mg, 0.6 mmol), and the mixture was shaken at roomtemperature for 16 h. The mixture was partitioned between EtOAc and H₂O.The organic phase was dried over MgSO₄, filtered, and evaporated. To theresultant crude oil Et₂O (3.5 mL) was added and a precipitate formedwhich was collected by filtration. The title compound was isolated as awhite solid (37 mg, 23%): mp 193-194° C.; ¹H NMR (300 MHz, DMSO-d₆) δ8.67 (s, 1H), 8.07 (d, J=6.3 Hz, 1H), 5.60 (s, 2H), 3.22 (s, 3H), 3.09(s, 3H), 1.11 (s, 9H); ESIMS m/z 299 ([M+H]⁺).

Compound 13 in Table 1 was synthesized as in Example 7.

Example 8 Preparation of4-amino-1-(benzyloxymethyl)-5-fluoropyrimidin-2(1H)-one (14) and1-(benzyloxymethyl)-4-(benzyloxymethylamino)-5-fluoropyrimidin-2(1H)-one(15)

A 25 mL Schlenk-type flask was charged with4-amino-5-fluoropyrimidin-2-ol (500 mg, 3.87 mmol), CH₃CN (10 mL), andBSA (1.42 mL, 5.81 mmol). The resulting white suspension was then heatedat 65° C. After 90 min, the clear, colorless solution was cooled to roomtemperature and benzyl chloromethyl ether (1.07 mL, 7.72 mmol) wasadded, giving a cloudy white suspension. After stirring for 2 h at roomtemperature, the reaction mixture was concentrated in vacuo to give awhite residue which was purified by reverse phase column chromatographyyielding 4-amino-1-(benzyloxymethyl)-5-fluoropyrimidin-2(1H)-one (14;433 mg, 45%) as a white solid: mp 213-217° C.; ¹H NMR (400 MHz, CDCl₃) δ7.98 (d, J=6.5 Hz, 1H), 7.81 (br s, 1H), 7.56 (br s, 1H), 7.24-7.36 (m,5H), 5.11 (s, 2H), 4.54 (s, 2H); IR 3302 (s), 3082 (s), 2939 (w), 2869(w), 1688 (s), 1619 (s), 1522 (s), 1468 (m), 1333 (m), 1131 (w), 1054(m) cm¹; ESIMS m/z 250 ([M+H]⁺).

1-(Benzyloxymethyl)-4-(benzyloxymethylamino)-5-fluoropyrimidin-2(1H)-one(15; 16.5 mg, 1.2%) was obtained as a colorless oil byproduct in thesynthesis of 14: ¹H NMR (400 MHz, CDCl₃) δ 8.85 (t, J=5.8 Hz, 1H), 8.08(d, J=6.6 Hz, 1H), 7.22-7.39 (m, 10H), 5.15 (s, 2H), 4.87 (d, J=5.8 Hz,2H), 4.56 (s, 2H), 4.54 (s, 2H); IR 3248 (w), 3062 (w), 3031 (w), 1683(s), 1644 (m), 1569 (m), 1520 (s), 1454 (w), 1357 (w), 1328 (m), 1189(w), 1069 (m) cm⁻¹; ESIMS m/z 370 ([M+H]⁺).

Compounds 16-23 in Table I were synthesized as in Example 8.

Example 9 Preparation ofN-(5-fluoro-1-methylsulfanylmethyl-2-oxo-1,2-dihydropyrimidin-4-yl)-N,N-dimethylformamidine(24)

A 250 mL round bottom flask was charged withN-(5-fluoro-2-hydroxypyrimidin-4-yl)-N,N-dimethylformamidine (1.00 g,5.43 mmol) and DMF (55 mL) to give a white suspension. Solid potassiumtert-butoxide (1.07 g, 9.53 mmol) was added, and the resulting paleyellow suspension was allowed to stir under nitrogen at room temperaturefor 20 min. Chloromethyl methyl sulfide (682 microliters (μL), 8.14mmol) was then added, and the mixture was heated at 60° C. for 21 h. Thecrude reaction mixture was concentrated in vacuo at 55° C. to give anoff-white residue which was purified by reverse phase columnchromatography yieldingN-(5-fluoro-1-methylsulfanylmethyl-2-oxo-1,2-dihydropyrimidin-4-yl)-N,N-dimethylformamidine(36 mg, 25%) as a pale yellow solid: mp 132-136° C.; ¹H NMR (400 MHz,CDCl₃) δ 8.68 (s, 1H), 8.20 (d, J=3.2 Hz, 1H), 5.40 (s, 2H), 3.19 (s,3H), 3.07 (s, 3H), 2.20 (s, 3H); IR 2960 (w), 2926 (w), 1640 (s), 1582(s), 1447 (s), 1382 (m), 1319 (m), 1269 (m), 1108 (m), 1051 (m) cm⁻¹;ESIMS m/z 267 ([M+Na]⁺).

Example 10 Preparation of4-amino-5-fluoro-1-(4-methylbenzyl)-pyrimidin-2(1H)-one (25)

Step 1: To a magnetically stirred solution of4-amino-5-fluoropyrimidin-2-ol (4.00 g, 31.0 mmol) in DMF (100 mL) wasadded N,N-dimethylformamide dimethyl acetal (DMF-DMA; 4.00 g, 34.0mmol). The mixture was stirred at room temperature for 72 h, dilutedwith Et₂O (200 mL), and filtered. The solid product was washed withheptane to give(E)-N′-(5-fluoro-2-oxo-1,2-dihydropyrimidin-4-yl)-N,N-dimethylformimidamide(5.23 g, 92%) as a white solid: mp 240-243° C.; ¹H NMR (300 MHz,DMSO-d₆) δ 10.7 (br s, 1H), 8.59 (s, 1H), 7.7 (d, J=5.6 Hz, 1H), 3.18(s, 3H), 3.06 (s, 3H); ESIMS m/z 185 ([M+H]⁺), m/z 183 ([M−H]⁻).

Step 2: Powdered K₂CO₃ (325 mesh; 2.03 g, 14.7 mmol) was added to amixture of the product from Step 1 (1.35 g, 7.35 mmol) andα-bromo-p-xylene (1.36 g, 7.35 mmol) in DMF (20 mL), under N₂, at roomtemperature. The resultant white slurry was warmed to 80° C. Afterstirring at 80° C. for 2 h, the reaction mixture was cooled, dilutedwith EtOAc (150 mL) and the solution washed with H₂O (4×50 mL) andsaturated (satd) NaCl (1×50 mL). The organic phase was dried (Na₂SO₄),filtered and concentrated in vacuo to give 1.01 g of a light yellowsolid. The crude material was dissolved in a mixture of EtOAc/CH₂Cl₂ andtreated with Celite (3 g). The solvent was removed in vacuo and theresidue purified by normal phase chromatography (gradient, 0 to 100%EtOAc/hexanes) to remove the isomeric O-alkylated product. The columnwas then eluted with 90% CH₂Cl₂/10% CH₃OH to obtain the desiredN-alkylated product,N′-[5-fluoro-1-(4-methylbenzyl)-2-oxo-1,2-dihydropyrimidin-4-yl]-N,N-dimethylforamidine(0.668 g, 32%) as a white solid: mp 178-179° C.; ¹H NMR (300 MHz, CDCl₃)δ 8.82 (s, 1H), 7.22-7.15 (m, 4H), 4.97 (s, 2H), 3.18 (s, 3H), 3.17 (s,3H), 2.34 (s, 3H); ESIMS m/z 289 ([M+H]⁺).

Step 3: Zinc chloride (1.24 g, 9.12 mmol) was added to a mixture of theformamidine product from Step 2 (0.656 g, 2.28 mmol) in absolute EtOH(10 mL). The resultant mixture was heated to reflux under N₂. Themixture gradually turned into a light yellow, homogeneous solution.After refluxing for 90 min a precipitate had formed, and after 2 h, thereaction mixture was allowed to cool to room temperature and wasconcentrated in vacuo. The residue was treated with CH₂Cl₂ (75 mL,slightly turbid in appearance) and washed with H₂O (25 mL). As soon asH₂O was added a white precipitate formed in both layers in theseparatory funnel. The solid was removed by vacuum filtration. The solidwas washed with H₂O followed by Et₂O. After air-drying overnight thewhite solid (0.58 g) was treated with 1:1 CH₇C17/MeOH (˜70 mL) andheated to reflux (turbid mixture). The mixture was filtered and thefiltrate was concentrated in vacuo. The residual solid was slurried withhexanes/Et₂O (˜3:1) and isolated by vacuum filtration, air-dried andthen vacuum oven dried (70-80° C.) to giveN-(5-fluoro-2-hydroxypyrimidin-4-yl)-N,N-dimethylformamidine (0.417 g,78%) as a white powder: mp 291-293° C. dec; ¹H NMR (300 MHz, DMSO-d₆) δ8.03 (d, J=6.9 Hz, 1H), 7.62 (br s, 1H), 7.40 (br s, 1H), 7.17 (d, J=7.8Hz, 2H), 7.12 (d, J=8.1 Hz, 2H), 4.73 (s, 2H), 2.25 (s, 3H); ¹³C NMR(150 MHz, DMSO-d₆) δ 158.2, 154.8, 137.3, 136.3 (d, J=240 Hz), 135.3,131.1 (d, J=30.6 Hz), 129.7, 128.3, 51.8, 21.3; ESIMS m/z 234 ([M+H]⁺),m/z 232 ([M−H]⁻); IR 3298 (m, br), 3100 (m, br), 1685 (s), 1619 (s),1518 (s), 1447 (m), 1383 (m), 1343 (w), 1120 (w), 776 (w) cm⁻¹.

Example 11 Preparation of4-amino-5-fluoro-1-(4-iodobutyl)-1H-pyrimidin-2-one (26)

To a suspension of 4-amino-5-fluoropyrimidin-2-ol (0.50 g, 3.87 mmol) inacetonitrile (CH₃CN; 20 mL) was added BSA (1.58 g, 7.75 mmol), and themixture was heated to 70° C. for 1 h resulting in a clear solution.After cooling to room temperature, 1,4-diiodobutane (1.2 g, 3.87 mmol)was added, and the mixture was stirred for 16 h at room temperature andthen at 70° C. for 3 h. The solvent was evaporated and the residue waspurified by normal phase chromatography (24 g SiO₂; gradient, 0 to 15%MeOH/CH₂Cl₂) to give an orange oil. The oil was dissolved in EtOAc andthe solution was slowly cooled. The resulting solid was collected byfiltration, washed with additional EtOAc, and dried to give4-amino-5-fluoro-1-(4-iodobutyl)-1H-pyrimidin-2-one (0.52 g, 43%) as atan solid: mp 181-184° C.; ¹H NMR (400 MHz, DMSO-d₆) δ 8.56 (s, 2H),8.25 (d, J=6.7 Hz, 1H), 3.70 (t, J=6.7 Hz, 2H), 3.29 (t, J=6.7 Hz, 2H),1.73 (m, 4H); ESIMS m/z 312 ([M+H]⁺).

Example 12 Preparation of4-amino-5-fluoro-1-(4-[1,2,4]triazol-1-yl-butyl)-1H-pyrimidin-2-one (27)

To a mixture of 1,2,4-triazole (0.044 g, 0.64 mmol), potassium^(t)butoxide (KO^(t)Bu; 0.072 g, 0.64 mmol), and 18-crown-6 (18C6; 0.008g, 0.03 mmol) in CH₃CN (3.5 mL) was added4-amino-5-fluoro-1-(4-iodobutyl)-1H-pyrimidin-2-one (0.10 g, 0.32 mmol),and the mixture was warmed to 70° C. and stirred for 16 h. The resultinghomogeneous solution was concentrated in vacuo to give the crude productas a white solid. Purification by reverse phase chromatography (13 gC18; gradient, 0 to 20% CH₃CN/water) afforded4-amino-5-fluoro-1-(4-[1,2,4]triazol-1-yl-butyl)-1H-pyrimidin-2-one(0.023 g, 28%) as a white solid: mp 197-200° C.; ¹H NMR (400 MHz,DMSO-d₆) δ 8.50 (s, 1H), 7.94 (m, 2H), 7.56 (s, 1H), 7.35 (s, 1H), 4.19(t, J=6.9 Hz, 2H), 3.61 (t, J=7.0 Hz, 2H), 1.73 (m, 2H), 1.51 (m, 2H);ESIMS m/z 253 ([M+H]⁺), m/z 251 ([M−H]⁻).

Example 13 Preparation of 4-amino-5-fluoro-1-methylpyrimidin-2(1H)-one(28)

A 25 mL screw-top vial was charged with 4-amino-5-fluoropyrimidin-2-ol(151.0 mg, 1.17 mmol), K₂CO₃ (289.2 mg, 2.09 mmol), 18C6 (278.6 mg,0.901 mmol) and anhydrous DMF (10 mL). Methyl methanesulfonate (0.0814mL, 0.961 mmol) was added, and the resulting mixture was agitated on arotary shaker at 85° C. for 21 h. After cooling to room temperature, thecrude material was concentrated in vacuo and purified by reverse phasecolumn chromatography to afford4-amino-5-fluoro-1-methylpyrimidin-2(1H)-one (61.9 mg, 37%) as a beigesolid: mp 195° C. (dec.); ¹H NMR (400 MHz, DMSO-d₆) δ 7.94 (d, J=6.8 Hz,1H), 7.52 (s, 1H), 7.32 (s, 1H), 3.18 (s, 3H); ESIMS m/z 144 ([M+]⁺.

Compounds 29-33 were prepared as in Example 13.

Example 14 Preparation of(E)-N′-(1-ethyl-5-fluoro-2-oxo-1,2-dihydropyrimidin-4-yl)-N,N-dimethylformimidamide(34)

A 25 mL screw-top vial was charged with(E)-N′-(5-fluoro-2-hydroxypyrimidin-4-yl)-N,N-dimethylformimidamide(99.5 mg, 0.540 mmol), DMF (2 mL), and NaH (60% dispersion in mineraloil; 24.5 mg, 0.613 mmol) and was agitated on a rotary shaker at 50° C.for 40 min. After cooling to room temperature, carbon disulfide (0.036mL, 0.599 mmol) was added, and the reaction mixture was agitated on arotary shaker at room temperature for 90 min. At this point, iodoethane(0.052 mL, 0.650 mmol) was added, and the reaction mixture was furtheragitated at room temperature for 3.5 h, whereupon the crude mixture wasconcentrated in vacuo. The crude material was purified by normal phasechromatography (gradient, 0 to 30% MeOH/CH₂Cl₂) to afford(E)-N′-(1-ethyl-5-fluoro-2-oxo-1,2-dihydropyrimidin-4-yl)-N,N-dimethylformimidamide(105 mg, 67%) as a white solid: mp 157-160° C.; ¹H NMR (400 MHz,DMSO-d₆) δ 8.62 (s, 1H), 8.09 (d, J=6.2 Hz, 1H), 3.70 (q, J=7.1 Hz, 2H),3.20 (s, 3H), 3.07 (s, 3H), 1.18 (t, J=7.1 Hz, 3H); ESIMS m/z 213([M+H]⁺.

Compounds 35 and 36 were prepared as in Example 14.

Example 15 Preparation of1-(ethoxymethyl)-5-fluoro-4-(2-fluorobenzylamino)-pyrimidin-2(1H)-one(37)

A 25 mL screw-top vial was charged with5-fluoro-4-(2-fluorobenzylamino)pyrimidin-2-ol (49.7 mg, 0.210 mmol),CH₃CN (1 mL), and BSA (0.054 mL, 0.0221 mmol), and the mixture wasagitated on an rotary shaker at 65° C. for 30 min. After cooling to roomtemperature, (chloromethoxy)ethane (0.022 mL, 0.237 mmol) was added, andthe resulting mixture was agitated on a rotary shaker at roomtemperature for 16 h. The crude reaction mixture was concentrated invacuo and was purified by normal phase chromatography (gradient, 0 to25% MeOH/CH₂Cl₂) to afford1-(ethoxymethyl)-5-fluoro-4-(2-fluorobenzylamino)-pyrimidin-2(1H)-one(55.0 mg, 89%) as a yellow oil: ¹H NMR (400 MHz, DMSO-d₆) δ 8.60 (t,J=5.8 Hz, 1H), 8.05-7.95 (m, 1H), 7.40-7.26 (m, 2H), 7.26-7.10 (m, 2H),5.01 (s, 2H), 4.59 (d, J=5.9 Hz, 2H), 3.49 (q, J=7.0 Hz, 2H), 1.09 (dd,J=9.0, 5.0 Hz, 3H); ESIMS m/z 296 ([M+H]⁺), m/z 294 ([M−H]⁻).

Example 16 Preparation of5-fluoro-4-((2-fluorobenzyl)(methyl)amino)-1-(4-methylbenzyl)pyrimidin-2(1H)-one(38)

A 25 mL screw-top vial was charged with NaH (60% dispersion in mineraloil; 20.5 mg, 0.513 mmol) and DMF (2.5 mL).5-Fluoro-N-(2-fluorobenzyl)-2-(4-methylbenzyloxy)pyrimidin-4-amine (149mg, 0.436 mmol) was added, and the mixture was allowed to stir at roomtemperature. After 10 min, iodomethane (0.033 mL, 0.530 mmol) was added,and the resulting mixture was allowed to stir at room temperature for anadditional 28 h. After this time, the crude reaction mixture wasconcentrated in vacuo and purified by normal phase chromatography(gradient, 0 to 40% EtOAc/Hexanes) to afford5-fluoro-4-((2-fluorobenzyl)(methyl)amino)-1-(4-methylbenzyl)pyrimidin-2(1H)-one(119.7 mg, 77%) as a colorless oil: ¹H NMR (400 MHz, DMSO-d₆) δ 8.16 (d,J=9.5 Hz, 1H), 7.45-7.06 (m, 8H), 4.83 (s, 2H), 4.79 (s, 2H), 3.13 (d,J=3.3 Hz, 3H), 2.27 (s, 3H); ¹³C NMR (101 MHz, DMSO-d₆) δ 160.1 (d,J=244.4 Hz), 154.9 (d, J=7.1 Hz), 152.9, 136.8, 136.2 (d, J=243.2 Hz),134.2, 132.8 (d, J=37.3 Hz), 129.2 (d, J=8.2 Hz), 129.0, 128.7, 127.8,124.6 (d, J=3.4 Hz), 124.0 (d, J=14.5 Hz), 115.3 (d, J=21.0 Hz), 51.0,47.7, 37.2 (d, J=8.3 Hz), 20.6; ESIMS m/z 356 ([M+H]⁺).

Example 17 Preparation of4-amino-5-fluoro-1-(thiophen-3-yl)pyrimidin-2(1H)-one (39)

A) To a solution of phosphorus pentasulfide (102.6 g, 0.46 mol) indiglyme (1 L) was added 5-fluoropyrimidine-2,4(1H,3H)-dione (30 g, 0.23mol). Solid sodium hydrogen carbonate (NaHCO₃; 77.3 g, 1.04 mol) wasadded at a rate determined by the evolution of carbon dioxide. Thereaction mixture was stirred overnight at 110° C. The yellow mixture wascooled and poured into 1 L of cold water. The precipitated solid productwas isolated by filtration and purified by normal phase chromatography(gradient, 10 to 50% EtOAc/Petroleum ether) to give5-fluoro-4-thioxo-3,4-dihydropyrimidin-2(1H)-one (13.4 g, 40%) as ayellow solid: mp 254-255° C.; ¹H NMR (301 MHz, DMSO-d₆) δ 7.81 (d, J=4.0Hz, 1H); ESIMS m/z 145 ([M−H]⁻).

B) This material was prepared by the procedure described in Tetrahedron1985, 41, 5289-5293. To a solution of5-fluoro-4-thioxo-3,4-dihydropyrimidin-2(1H)-one (12.4 g, 84.9 mmol) andsodium methoxide (4.54 g, 84.9 mmol) in MeOH (100 mL) was added dropwiseallyl bromide (10.27 g, 84.9 mmol) at room temperature. The reactionmixture was stirred overnight at room temperature. After removal ofsolvent, the residue was purified by normal phase chromatography(gradient, 10 to 33% EtOAc/hexane), to give4-(allylthio)-5-fluoropyrimidin-2(1H)-one (6 g, 38%) as a white solid:mp 150-152° C.; ¹H NMR (301 MHz, DMSO-d₆) δ 11.60 (s, 1H), 8.00 (d,J=4.5 Hz, 1H), 5.90 (ddt, J=16.8, 10.0, 6.8 Hz, 1H), 5.34 (dd, J=16.9,1.4 Hz, 1H), 5.15 (dd, J=10.0, 0.7 Hz, 1H), 3.83 (d, J=6.8 Hz, 2H);ESIMS m/z 187 ([M+H]⁺).

C) This material was prepared by the procedure described in J. Org.Chem. 2006, 71, 9183-9190. To a stirred suspension of dry Cu(OAc)₂ (1.02g, 5.64 mmol), 4-(allylthio)-5-fluoro-pyrimidin-2(1H)-one (700 mg, 3.76mmol), thiophen-3-ylboronic acid (962 mg, 7.52 mmol), and activated 3 Åmolecular sieves (2 g) in dry CH₂Cl₂ (30 mL) was added pyridine (595 mg,7.52 mmol) at room temperature. The mixture was stirred for 24 h atambient temperature in the presence of air. The reaction mixture wasdiluted with CH₂Cl₂ (30 mL), filtered through a pad of Celite, andwashed with water (50 mL) in the presence of ethylenediaminetetraaceticacid (EDTA; 700 mg, 2.4 mmol). The colorless organic phase was driedover MgSO₄ and was concentrated in vacuo. The residue was purified bynormal phase chromatography (isocratic, 2:1 petroleum ether:EtOAc) toafford 4-(allylthio)-5-fluoro-1-(thiophen-3-yl)pyrimidin-2(1H)-one (290mg, 29%) as a yellow solid: mp 125-127° C.; ¹H NMR (301 MHz, DMSO-d₆) δ8.52-8.35 (m, 1H), 7.81 (s, 1H), 7.69-7.55 (m, 1H), 7.32 (d, J=3.5 Hz,1H), 6.05-5.81 (m, 1H), 5.36 (d, J=16.9 Hz, 1H), 5.18 (d, J=9.8 Hz, 1H),3.89 (d, J=6.4 Hz, 2H); ESIMS m/z 269 ([M+H]⁺).

D) This material was prepared by the procedure described in J. Org.Chem. 2006, 71, 9183-9190.4-(Allylthio)-5-fluoro-1-(thiophen-3-yl)pyrimidin-2(1H)-one (330 mg,1.23 mmol) was dissolved in a methanol solution of ammonia (7 N, 5 mL).The reaction mixture was stirred overnight at 100° C. in a pressurevessel. After removal of solvent, the residue was purified bypreparative thin layer chromatography to give4-amino-5-fluoro-1-(thiophen-3-yl)pyrimidin-2(1H)-one (177 mg, 68%) as ayellow solid: mp 228-229° C.; ¹H NMR (300 MHz, DMSO-d₆) δ 8.11 (d, J=6.9Hz, 1H), 7.89 (s, 1H), 7.65 (d, J=1.9 Hz, 2H), 7.56 (dd, J=5.1, 3.3 Hz,1H), 7.29 (dd, J=5.1, 1.0 Hz, 1H); ESIMS m/z 212 ([M+H]⁺).

Compounds 40-55 were prepared as described in Example 17.

Example 18 Preparation of(E)-N′-(5-fluoro-2-oxo-1-(thiophen-3-yl)-1,2-dihydropyrimidin-4-yl)-N,N-dimethylformimidamide(56)

4-Amino-5-fluoro-1-(thiophen-3-yl)pyrimidin-2(1H)-one (140 mg, 0.66mmol) was dissolved in DMF-DMA (5 mL). The reaction mixture was stiffedat reflux overnight. The residual DMF-DMA was removed in vacuo, and theresidue was purified by preparative thin layer chromatography to give(E)-N′-(5-fluoro-2-oxo-1-(thiophen-3-yl)-1,2-dihydropyrimidin-4-yl)-N,N-dimethylformimidamide(75 mg, 43%) as a yellow solid: mp 211-213° C.; ¹H NMR (300 MHz,DMSO-d₆) δ 8.73 (s, 1H), 8.22 (d, J=6.4 Hz, 1H), 7.75 (dd, J=3.2, 1.4Hz, 1H), 7.60 (dd, J=5.2, 3.2 Hz, 1H), 7.34 (dd, J=5.2, 1.4 Hz, 1H),3.26 (s, 3H), 3.13 (s, 2H); ESIMS m/z 267 ([M+H]⁺).

Compounds 57-64 were prepared as described in Example 18.

Example 19 Preparation of5-fluoro-4-(2-fluorobenzylamino)-1-(thiophen-3-yl)pyrimidin-2(1H)-one(65)

To a solution of4-(allylthio)-5-fluoro-1-(thiophen-3-yl)pyrimidin-2(1H)-one (140 mg,0.66 mmol) in MeOH (1 mL) was added (2-fluorophenyl)methanamine (50 mg,0.186 mmol). The reaction mixture was heated at 100° C. for 30 min in amicrowave. After cooling, the mixture was purified by preparative thinlayer chromatography to give5-fluoro-4-(2-fluorobenzylamino)-1-(thiophen-3-yl)pyrimidin-2(1H)-one(41 mg, 20%) as a white solid: mp 75-78° C.; ¹H NMR (300 MHz, DMSO-d₆) δ8.70 (s, 1H), 8.16 (d, J=7.0 Hz, 1H), 7.66 (dd, J=3.2, 1.4 Hz, 1H), 7.57(dd, J=5.2, 3.2 Hz, 1H), 7.43-7.13 (m, 5H), 4.63 (d, J=5.5 Hz, 2H);ESIMS m/z 320 ([M+H]⁺).

Compounds 66-73 were prepared as described in Example 19.

Example 20 Preparation of4-amino-1-(cyclopropylmethyl)-5-fluoropyrimidin-2(1H)-one (74)

To a solution of (bromomethyl)cyclopropane (1.0 g, 7.4 mmol) in DMF (20mL) was added molecular sieves (˜2 g), and the resulting mixture wasstirred at room temperature. After 1 h, 4-amino-5-fluoropyrimidin-2-ol(1.9 g, 14.8 mmol) and K₂CO₃ (5.1 g, 37 mmol) were added, and thereaction mixture was heated at 90° C. for 12 h. After cooling to roomtemperature, the crude reaction mixture was filtered through a Büchnerfunnel, and the solid residue was washed with EtOAc. The collectedfiltrate was concentrated in vacuo to give a residue which was purifiedby normal phase chromatography (isocratic, 5% MeOH/EtOAc). Followingrecrystallization from methyl tert-butylether,4-amino-1-(cyclopropylmethyl)-5-fluoropyrimidin-2(1H)-one (1.12 g, 83%)was isolated as a white solid: mp 224-226° C.; ¹H NMR (400 MHz,methanol-d₄) δ 7.86 (d, J=6.2 Hz, 1H), 3.61 (d, J=7.2 Hz, 2H), 1.24(ddd, J=12.8, 7.6, 4.8 Hz, 1H), 0.65-0.50 (m, 2H), 0.39 (q, J=4.8 Hz,2H); ESIMS m/z 184 ([M+H]⁺).

Compounds 75-79 were prepared as described in Example 20.

Example 21 Preparation of ethyl1-(cyclopropylmethyl)-5-fluoro-2-oxo-1,2-dihydropyrimidin-4-ylcarbamate(80)

4-Amino-1-(cyclopropylmethyl)-5-fluoropyrimidin-2(1H)-one (200 mg, 1.09mmol) was dissolved in CH₂Cl₂ (0.90 mL) and pyridine (172.4 mg, 2.18mmol) at room temperature and then was cooled to −20° C. Ethylchloroformate (166 mg, 1.53 mmol) was then added to the reaction mixturedropwise, keeping the reaction temperature between −20 and −5° C. Afterthe addition was complete, the reaction was allowed to warm slowly toroom temperature and stirred for 2 h. The reaction mixture was filtered,and the solids were rinsed with EtOAc (15 mL×3). The filtrate wasconcentrated in vacuo, and purified by preparative thin layerchromatography, to afford ethyl1-(cyclopropylmethyl)-5-fluoro-2-oxo-1,2-dihydropyrimidin-4-ylcarbamate(70 mg, 30%) as a pale yellow solid: mp 90-92° C.; ¹H NMR (400 MHz,methanol-d₄) δ 8.20 (s, 1H), 4.26 (q, J=7.1 Hz, 2H), 3.70 (d, J=7.2 Hz,2H), 1.24-1.36 (m, 4H), 0.65-0.57 (m, 2H), 0.46-0.39 (m, 2H); ESIMS m/z256 ([M+H]⁺).

Compounds 81-84 were prepared as described in Example 21.

Example 22 Preparation of1-(2-chlorophenyl)-3-(1-(cyclopropylmethyl)-5-fluoro-2-oxo-1,2-dihydropyrimidin-4-yl)urea(85)

To a stirred solution of4-amino-1-(cyclopropylmethyl)-5-fluoropyrimidin-2(1H)-one (150 mg, 0.819mmol) in dry CH₃CN (7.5 mL) at room temperature and under nitrogen wasadded 2-chlorophenylisocyanate (138.3 mg, 0.90 mmol). After stirring for1 h, the crude reaction mixture was filtered, and the solids were rinsedwith CH₃CN (10 mL). The collected filtrate was then concentrated invacuo and dried under high vacuum to afford1-(2-chlorophenyl)-3-(1-(cyclopropylmethyl)-5-fluoro-2-oxo-1,2-dihydropyrimidin-4-yl)urea(160 mg, 58%) as an off-white solid: mp 197-199° C.; ¹H NMR (400 MHz,methanol-d₄) δ 8.26 (d, J=6.0 Hz, 1H), 8.21 (dd, J=8.3, 1.5 Hz, 1H),7.47 (dd, J=8.0, 1.4 Hz, 1H), 7.35-7.28 (m, 1H), 7.13 (td, J=7.8, 1.5Hz, 1H), 3.74 (d, J=7.3 Hz, 2H), 1.32 (m, 1H), 0.69-0.58 (m, 2H),0.50-0.38 (m, 2H); ESIMS m/z 337 ([M+H]⁺).

Compounds 86-93 were prepared as described in Example 22.

Example 23 Preparation ofN-(5-fluoro-2-oxo-1-((tetrahydrofuran-2-yl)methyl)-1,2-dihydropyrimidin-4-yl)thiophene-2-carboxamide(94)

This material was prepared by the procedure described in J. Org. Chem.2005, 70, 7459-7467. To a solution of4-amino-5-fluoro-1-((tetrahydrofuran-2-yl)methyl)pyrimidin-2(1H)-one(200 mg, 0.94 mmol) in dry THF (1 mL) at room temperature were added1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC; 180 mg, 0.94 mmol)and 1H-benzo[d][1,2,3]triazol-1-ol (HOBt; 139 mg, 1.03 mmol). Afterstirring for 10 min, thiophene-2-carboxylic acid (145 mg, 1.13 mmol) wasadded, and the resulting solution was allowed to stir at roomtemperature for 12 h. The reaction mixture was concentrated in vacuo,quenched with satd aq NaHCO₃ solution (10 mL), and extracted with EtOAc(25 mL×3). The combined extracts were washed with satd aq sodiumchloride (NaCl) solution, dried over Na₂SO₄, filtered, and concentratedby rotary evaporation. Purification by normal phase chromatography(gradient, 0 to 2% MeOH/CH₂Cl₂) afforded4-amino-5-fluoro-1-((tetrahydrofuran-2-yl)methyl)pyrimidin-2(1H)-one (60mg, 20%) as a white solid: mp 168-170° C.; ¹H NMR (400 MHz, CDCl₃) δ12.96 (s, 1H), 7.96 (d, J=3.7 Hz, 1H), 7.63 (d, J=5.7 Hz, 1H), 7.60 (d,J=4.9 Hz, 1H), 7.16-7.11 (m, 1H), 4.20-4.08 (m, 2H), 3.89 (dd, J=15.1,6.9 Hz, 1H), 3.80 (dd, J=14.5, 7.5 Hz, 1H), 3.57 (dd, J=14.4, 7.7 Hz,1H), 2.10 (dt, J=12.8, 6.7 Hz, 1H), 1.99-1.87 (m, 2H), 0.88 (m, 1H);ESIMS Ink 324 ([M+H]⁺).

Compounds 95-101 were prepared as described in Example 23.

Example 24 Preparation of5-fluoro-1-((tetrahydrofuran-2-yl)methyl)-4-(thiophen-2-ylmethylamino)pyrimidin-2(1H)-one(102)

This material was prepared by the procedure described in J. Org. Chem.2005, 70, 7459-7467. To a solution of4-amino-5-fluoro-1-((tetrahydrofuran-2-yl)methyl)pyrimidin-2(1H)-one(160 mg, 0.495 mmol) in THF (4 mL) at room temperature was added BSA(0.61 mL, 2.47 mmol) dropwise. After the addition was complete,borane-N,N-diisopropylethylamine complex (DIPEA.BH₃; 0.90 mL, 4.95 mL)was added dropwise, and the resulting solution was stirred at roomtemperature for 15 min. The reaction mixture was quenched by theaddition of MeOH (20 mL), and the mixture was concentrated in vacuo. Theresulting mixture was dissolved in a 1:1 (v:v) mixture of 17% ammonia inmethanol:28% ammonia in water (135 mL) and heated at 50° C. for 13 h.After cooling to room temperature, the mixture was extracted withchloroform (CHCl₃; 100 mL×2). The combined extracts were washed with aqNaCl solution, dried over Na₂SO₄, filtered, and concentrated in vacuo.Purification by preparative thin layer chromatography afforded5-fluoro-1-((tetrahydrofuran-2-yl)methyl)-4-(thiophen-2-ylmethylamino)pyrimidin-2(1H)-one(40 mg, 26%) as a gummy white solid: ¹H NMR (400 MHz, acetone-d₆) δ 7.69(d, J=6.7 Hz, 1H), 7.52 (s, 1H), 7.32 (dd, J=5.1, 1.2 Hz, 1H), 7.08 (dd,J=3.4, 0.9 Hz, 1H), 6.95 (dd, J=5.1, 3.5 Hz, 1H), 4.85 (d, J=6.0 Hz,2H), 4.12 (ddd, J=14.6, 7.1, 3.2 Hz, 1H), 4.00 (dd, J=13.6, 2.8 Hz, 1H),3.83 (dt, J=8.1, 6.7 Hz, 1H), 3.72-3.64 (m, 1H), 3.56 (dd, J=13.6, 7.7Hz, 1H), 2.02-1.93 (m, 1H), 1.86 (ddd, J=11.0, 8.1, 1.6 Hz, 2H),1.67-1.54 (m, 1H); IR (thin film) 3222, 3125, 3068, 2950, 2875, 1673,1623, 1586, 1556, 1508, 1368, 1329, 1186, 1139, 1065, 906 cm⁻¹; ESIMSm/z 310 ([M+H]⁺).

Compounds 103 and 104 were prepared as described in Example 24.

Example 25 Preparation of5-fluoro-4-(2-fluorobenzylamino)-1-isobutylpyrimidin-2(1H)-one (105)

A) To a solution of 5-fluoropyrimidine-2,4(1H,3H)-dione (5.0 g, 38 mmol)and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU; 6.4 g, 42 mmol) in dryCH₃CN (150 mL) at room temperature and under nitrogen was added1-bromo-2-methylpropane (5.3 g, 38 mmol) dropwise. The reaction was thenheated to reflux for 18 h. After cooling to room temperature, thesolvent was removed in vacuo. The crude residue was purified by normalphase chromatography (gradient, 0 to 20% EtOAc/Petroleum ether),providing 5-fluoro-1-isobutylpyrimidine-2,4(1H,3H)-dione (2.5 g, 35%) asa white solid: mp 173-174° C.; ¹H NMR (400 MHz, CDCl₃) δ 8.61 (s, 1H),7.21 (d, J=5.5 Hz, 1H), 3.53 (d, J=7.5 Hz, 2H), 2.13-2.01 (m, 1H), 0.98(d, J=6.7 Hz, 6H); ESIMS m/z 185 ([M−H]⁻).

B) Phosphoryl trichloride (3.3 g, 21 mmol) was added to a solution of1,2,4-triazole (6.7 g, 97 mmol) in CH₃CN (53 mL) under nitrogen at roomtemperature. The mixture was cooled to 0° C., whereupon triethylamine(Et₃N, 9.5 g, 92 mmol) was added dropwise followed by the addition of asolution of 5-fluoro-1-isobutylpyrimidine-2,4(1H,3H)-dione (2.0 g, 11mmol) in CH₃CN (30 mL). After stiffing for 1 h at room temperature, Et₃N(3.6 g, 36 mmol) and then water (5 mL, 280 mmol) were added, and thereaction mixture was stirred for an additional 10 min. The crudereaction mixture was then concentrated in vacuo. Recrystallization fromEtOAc/petroleum ether provided5-fluoro-1-isobutyl-4-(1H-1,2,4-triazol-1-yl)pyrimidin-2(1H)-one (1.9 g,74%) as an off white crystalline solid: mp 150-153° C.; ¹H NMR (400 MHz,CDCl₃) δ 9.26 (s, 1H), 8.23 (s, 1H), 7.84 (d, J=5.7 Hz, 1H), 3.79 (d,J=7.4 Hz, 2H), 2.28 (dt, J=13.7, 6.9 Hz, 1H), 1.02 (d, J=6.7 Hz, 6H);ESIMS m/z 238 ([M+H]⁺).

C) A solution of5-fluoro-1-isobutyl-4-(1H-1,2,4-triazol-1-yl)pyrimidin-2(1H)-one (500mg, 2.1 mmol) and 2-fluorobenzylamine (313 mg, 2.5 mmol) in dry1,4-dioxane (10 mL) was heated to reflux for 1 h under nitrogen. Aftercooling to room temperature, the reaction mixture was concentrated invacuo. Recrystallization from EtOAc/methyl tert-butylether afforded5-fluoro-4-(2-fluorobenzylamino)-1-isobutylpyrimidin-2(1H)-one (545 mg,89%) as an off white solid: mp 118-119° C.; ¹H NMR (400 MHz, CDCl₃) δ7.45 (td, J=7.6, 1.7 Hz, 1H), 7.35-7.28 (m, 2H), 7.13 (ddd, J=21.9,13.9, 7.3 Hz, 3H), 5.58 (s, 1H), 4.81 (d, J=5.4 Hz, 2H), 3.56 (d, J=7.5Hz, 2H), 2.16 (dt, J=13.6, 6.8 Hz, 1H), 0.95 (d, J=6.7 Hz, 6H); ESIMSink 295 ([M+H]⁺).

Compounds 106-110 were prepared as described for Example 25.

TABLE I Compounds and Related Characterization Data ¹H NMR^(a) CmpdStructure Appearance mp (° C.) MS (δ, solvent)  3

white solid 157-187 dec (CDCl₃) 7.47 (d, J = 6.1 Hz, 1H), 5.91 (s, 1H),4.45 (s, 2H), 4.38 (d, J = 5.2 Hz, 2H), 2.36 (s, 12H)  5

yellow oil ESIMS m/z 343 ([M + H]⁺) (CDCl₃) 8.81 (s, 1H), 7.40 (d, J =2.3 Hz, 1H), 7.37 (d, J = 8.2 Hz, 1H), 7.33 (d, J = 5.6 Hz, 1H), 7.22(dd, J = 8.2, 2.3 Hz, 1H), 5.06 (s, 2H), 3.18 (s, 6H)  6

white solid 186-188 ESIMS m/z 275 ([M + H]⁺) (CDCl₃) 8.85 (s, 1H),7.41-7.31 (m, 5H), 7.24 (d, J = 5.5 Hz, 1H), 5.04 (s, 2H), 3.22 (s, 1H),3.21 (s, 3H)  7

white solid 178-179 ESIMS m/z 289 ([M + H]⁺) (CDCl₃) 8.85 (s, 1H),7.26-7.17 (m, 5H), 4.99 (s, 2H), 3.21 (s, 6H), 2.37 (s, 3H)  13

white solid 109-111 ESIMS m/z 285 ([M + H]⁺) (600 MHz, DMSO- d₆) 8.65(s, 1H), 8.04 (d, J = 6.2 Hz, 1H), 5.58 (s, 2H), 3.20 (s, 3H), 3.07 (s,3H), 2.27 (t, J = 7.3 Hz, 2H), 1.53- 1.46 (m, 2H), 0.83 (t, J = 7.3 Hz,3H)  16

white solid 160-163 ESIMS m/z 218 ([M + H]⁺) (DMSO-d₆) 7.97 (d, J = 6.6Hz, 1H), 7.83 (s, 1H), 7.58 (s, 1H), 5.03 (s, 2H), 3.65-3.53 (m, 2H),3.46-3.38 (m, 2H), 3.22 (s, 3H)  17

off-white solid 187-192 ESIMS m/z 260 ([M + H]⁺) (DMSO-d₆) δ 7.96 (d, J= 6.6 Hz, 1H), 7.80 (s, 1H), 7.57 (s, 1H), 4.99 (s, 2H), 3.51 (dd, J =20.2, 12.2 Hz, 2H), 0.85 (t, J = 7.9 Hz, 2H), −0.03 (s, 9H).  18

off-white solid 166-170 ESIMS m/z 272 ([M + H]⁺) (DMSO-d₆) 7.98 (d, J =6.5 Hz, 1H), 7.85 (s, 1H), 7.62 (s, 1H), 5.01 (s, 2H), 3.44 (t, J = 6.4Hz, 2H), 1.47 (m, 2H), 1.24 (m, 10H), 0.86 (t, J = 5.9 Hz, 3H)  19

white 240-245 ESIMS m/z 270 ([M + H]⁺) (DMSO-d₆) 8.09 (d, J = 6.6 Hz,1H), 7.97 (s, 1H), 7.72 (s, 1H), 7.36 (d, J = 8.8 Hz, 2H), 7.07 (d, J =8.9 Hz, 2H), 5.58 (s, 2H)  20

white solid 150-154 ESIMS m/z 260 ([M + H]⁺) (DMSO-d₆) 7.97 (s, 1H),7.81 (d, J = 6.3 Hz, 1H), 7.72 (s, 1H), 5.84 (s, 1H), 4.15 (dd, J =13.7, 6.8 Hz, 2H), 3.59 (dd, J = 13.3, 6.4 Hz, 2H), 1.28- 1.04 (m, 6H) 21

white solid 210-214 ESIMS m/z 230 ([M + H]⁺) (DMSO-d₆) 7.99 (m, J = 6.7Hz, 2H), 7.72 (s, 1H), 5.55 (s, 2H), 2.30 (t, J = 7.2 Hz, 2H), 1.68-1.39(m, 2H), 0.86 (t, J = 7.4 Hz, 3H)  22

white solid 259-264 ESIMS m/z 244 ([M + H]⁺) (DMSO-d₆) 7.99 (d, J = 6.7Hz, 1H), 7.97 (s, 1H), 7.71 (s, 1H), 5.54 (s, 2H), 1.12 (s, 9H)  23

white solid 162-166 ESIMS m/z 246 ([M + H]⁺) (DMSO-d₆) 8.08 (d, J = 7.0Hz, 1H), 7.95 (s, 1H), 7.69 (s, 1H), 6.72 (q, J = 5.2 Hz, 1H), 4.12 (q,J = 7.0 Hz, 2H), 1.55 (d, J = 6.1 Hz, 3H), 1.20 (t, J = 7.1 Hz, 3H)  29

white solid 279 dec ESIMS m/z 158 ([M + H]⁺) (DMSO-d₆) 7.98 (d, J = 6.8Hz, 1H), 7.57 (s, 1H), 7.39 (s, 1H), 3.63 (q, J = 7.1 Hz, 2H), 1.14 (t,J = 7.1 Hz, 3H)  30

white solid 168-189 ESIMS m/z 264 ([M + H]⁺) (DMSO-d₆) 7.93 (d, J = 3.3Hz, 1H), 7.31 (s, 2H), 7.19 (d, J = 8.6 Hz, 2H), 6.90-6.82 (m, 2H), 4.28(t, J = 6.9 Hz, 2H), 3.72 (s, 3H), 2.89 (t, J = 6.9 Hz, 2H)  31

white solid 252-254 ESIMS m/z 268 ([M + H]⁺) (DMSO-d₆) 7.97 (d, J = 3.5Hz, 1H), 7.46 (s, 2H), 7.39- 7.34 (m, 2H), 7.34- 7.28 (m, 2H), 4.34 (t,J = 6.7 Hz, 2H), 2.97 (t, J = 6.7 Hz, 2H)  32

pale yellow solid 255 dec ESIMS m/z 214 ([M + H]⁺) (DMSO-d₆) 7.92 (d, J= 3.2 Hz, 1H), 7.27 (s, 2H), 4.10 (dd, J = 10.5, 6.7 Hz, 1H), 4.02 (dd,J = 10.5, 8.0 Hz, 1H), 3.78-3.69 (m, 2H), 3.63 (dd, J = 15.0, 7.8 Hz,1H), 3.47 (dd, J = 8.6, 5.6 Hz, 1H), 2.59 (dt, J = 14.1, 7.2 Hz, 1H),1.97 (dtd, J = 13.8, 8.2, 5.6 Hz, 1H), 1.65-1.53 (m, 1H)  33

beige solid 250-254 ESIMS m/z 256 ([M + H]⁺) (DMSO-d₆) 8.04 (d, J = 6.6Hz, 1H), 7.74 (s, 1H), 7.50 (s, 1H), 7.35-7.20 (m, 2H), 7.06 (td, J =8.5, 1.8 Hz, 1H), 4.82 (s, 2H)  35

white solid 196-200 ESIMS m/z 311 ([M + H]⁺) (DMSO-d₆) 8.64 (s, 1H),8.24 (d, J = 6.2 Hz, 1H), 7.48- 7.35 (m, 2H), 7.23- 7.13 (m, 1H), 4.85(s, 2H), 3.21 (s, 3H), 3.08 (s, 3H)  36

white solid 196-199 ESIMS m/z 271 ([M + H]⁺) (DMSO-d₆) 8.67 (s, 1H),8.05 (d, J = 6.2 Hz, 1H), 4.48 (s, 2H), 4.14 (q, J = 7.1 Hz, 2H), 3.22(s, 3H), 3.10 (s, 3H), 1.20 (t, J = 7.1 Hz, H)  40

white solid 244.8-245.6 ESIMS m/z 266 ([M + H]⁺) (DMSO-d₆) 7.98 (d, J =6.7 Hz, 1H), 7.80 (s, 1H), 7.57 (s, 1H), 7.00 (m, 2H), 6.89 (dd, J =8.6, 2.3 Hz, 1H), 3.79 (s, 3H), 3.76 (s, 3H)  41

white solid 213.5-214.4 ESIMS m/z 156 ([M + H]⁺) (DMSO-d₆) 8.28 (d, J =7.1 Hz, 1H), 8.01 (s, 1H), 7.77 (s, 1H), 7.18 (dd, J = 15.4, 10.3 Hz,1H), 5.27 (d, J = 16.2 Hz, 1H), 4.78 (d, J = 8.0 Hz, 1H)  42

off-white solid 233-235 ESIMS m/z 206 ([M + H]⁺) (DMSO-d₆) 8.05 (dd, J =6.8, 1.7 Hz, 1H), 7.86 (s, 1H), 7.62 (s, 1H), 7.51-7.31 (m, 5H)  43

off-white solid 225-227 ESIMS m/z 220 ([M + H]⁺) (DMSO-d₆) 8.00 (d, J =6.7 Hz, 1H), 7.83 (s, 1H), 7.59 (s, 1H), 7.25 (s, 4H), 2.34 (s, 3H)  44

brown solid 230-232 ESIMS m/z 236 ([M + H]⁺) (DMSO-d₆) 7.99 (d, J = 6.7Hz, 1H), 7.81 (s, 1H), 7.57 (s, 1H), 7.29 (d, J = 8.8 Hz, 2H), 6.98 (d,J = 8.8 Hz, 2H), 3.78 (s, J = 8.6 Hz, 3H)  45

off-white solid 255-257 ESIMS m/z 240 ([M + H]⁺) (DMSO-d₆) 8.07 (d, J =6.3 Hz, 1H), 7.93 (s, 1H), 7.68 (s, 1H), 7.51 (dd, J = 8.6, 1.0 Hz, 2H),7.43 (dd, J = 8.7, 1.1 Hz, 2H)  46

pale brown solid 175-178 ESIMS m/z 231 ([M + H]⁺) (DMSO-d₆) 8.16 (d, J =6.9 Hz, 1H), 7.98-7.94 (m, 1H), 7.86-7.82 (m, 1H), 7.82-7.76 (m, 1H),7.67 (d, J = 8.0 Hz, 1H)  47

off-white solid 275-279 ESIMS m/z 250 ([M + H]⁺) (DMSO-d₆) 7.96 (d, J =6.7 Hz, 1H), 7.82 (s, 1H), 7.57 (s, 1H), 6.99 (d, J = 2.1 Hz, 1H), 6.96(d, J = 8.2 Hz, 1H), 6.82 (dd, J = 8.3, 2.1 Hz, 1H), 6.08 (s, 2H)  48

yellow solid 256-258 ESIMS m/z 232 ([M + H]⁺) (DMSO-d₆) δ 8.42 (d, J =7.2 Hz, 1H), 8.04 (s, 1H), 7.82 (s, 1H), 7.66 (d, J = 15.0 Hz, 1H), 7.44(d, J = 7.9 Hz, 2H), 7.36 (t, J = 7.6 Hz, 2H), 7.26 (dd, J = 10.5, 4.0Hz, 1H), 6.81 (d, J = 15.0 Hz, 1H)  49

pale brown solid 212-214 ESIMS m/z 246 ([M + H]⁺) (DMSO-d₆) 8.24 (d, J =7.2 Hz, 1H), 7.92 (s, 1H), 7.69 (s, 1H), 7.31 (m, 2H), 7.22 (dd, J =14.9, 7.1 Hz, 3H), 7.03 (dd, J = 14.5, 1.6 Hz, 1H), 5.95 (dt, J = 14.5,7.3 Hz, 1H), 3.45 (d, J = 7.1 Hz, 2H)  50

off-white solid 244.4-245.7 ESIMS m/z 284 ([M + H]⁺) (DMSO-d₆) 8.14 (d,J = 6.8 Hz, 1H), 8.04-7.92 (m, 3H), 7.75 (s, J = 7.8 Hz, 1H), 7.69 (d, J= 8.4 Hz, 2H), 3.26 (s, 3H).  51

white solid 190.6-192.7 ESIMS m/z 210 ([M + H]⁺) (DMSO-d₆) 7.75 (d, J =6.6 Hz, 1H), 7.62 (s, 1H), 7.41 (s, 1H), 5.66 (t, J = 3.7 Hz, 1H), 2.15(d, J = 36.9 Hz, 4H), 1.60 (dt, J = 10.5, 5.0 Hz, 4H)  52

yellow solid 211.2-213.0 ESIMS m/z 232 ([M + H]⁺) (DMSO-d₆) 7.97 (d, J =6.5 Hz, 1H), 7.83 (s, 1H), 7.60 (s, 1H), 7.45-7.24 (m, 5H), 5.86 (d, J =0.9 Hz, 1H), 5.37 (d, J = 0.9 Hz, 1H)  53

white solid 152.8-153.4 ESIMS m/z 198 ([M + H]⁺) (DMSO-d₆) 8.17 (d, J =7.1 Hz, 1H), 7.85 (s, 1H), 7.62 (s, 1H), 6.88 (d, J = 14.5 Hz, 1H), 5.74(dt, J = 14.3, 7.1 Hz, 1H), 2.06 (q, J = 7.1 Hz, 2H), 1.48- 1.31 (m,2H), 0.89 (t, J = 7.3 Hz, 3H)  54

yellow solid 263.3-265.1 ESIMS m/z 262 ([M + H]⁺) (CD₃OD) 8.20 (d, J =6.7 Hz, 1H), 7.55 (dd, J = 14.8, 1.9 Hz, 1H), 7.40 (d, J = 8.7 Hz, 2H),6.94-6.87 (m, 2H), 6.68 (d, J = 14.7 Hz, 1H), 3.80 (s, 3H)  55

white solid 272.8-274.2 ESIMS m/z 256 ([M + H]⁺) (DMSO-d₆) 8.17 (d, J =6.7 Hz, 1H), 8.00-7.85 (m, 5H), 7.65 (s, 1H), 7.61- 7.49 (m, 3H)  57

yellow solid 196.1-198.0 ESIMS m/z 321 ([M + H]⁺) (DMSO-d₆) 8.72 (s,1H), 8.09 (d, J = 6.2 Hz, 1H), 7.07- 7.02 (m, 1H), 7.00 (s, 1H), 6.94(dd, J = 8.5, 2.3 Hz, 1H), 3.80 (s, 3H), 3.77 (s, 3H), 3.25 (s, 3H),3.13 (s, 3H)  58

yellow solid 179.6-181.3 ESIMS m/z 211 ([M + H]⁺) (DMSO-d₆) 8.69 (d, J =17.4 Hz, 1H), 8.37 (d, J = 6.6 Hz, 1H), 7.21 (ddd, J = 22.7, 11.3, 6.8Hz, 1H), 5.41 (d, J = 16.2 Hz, 1H), 4.89 (d, J = 9.2 Hz, 1H), 3.25 (s,3H), 3.11 (d, J = 11.5 Hz, 3H)  59

white solid 284.6-186.9 ESIMS m/z 339 ([M + H]⁺) (DMSO-d₆) 8.75 (s, 1H),8.23 (d, J = 6.3 Hz, 1H), 8.01 (d, J = 8.6 Hz, 2H), 7.74 (d, J = 8.6 Hz,2H), 3.27 (s, 3H), 3.26 (s, 3H), 3.14 (s, 3H)  60

white solid 173.2-174.4 ESIMS m/z 265 ([M + H]⁺) (DMSO-d₆) 8.63 (s, 1H),7.87 (d, J = 6.0 Hz, 1H), 5.72 (s, 1H), 3.21 (s, 3H), 3.08 (s, 3H), 2.18(d, J = 37.4 Hz, 4H), 1.62 (dd, J = 29.1, 4.7 Hz, 4H)  61

yellow solid 147.0-147.9 ESIMS m/z 287 ([M + H]⁺) (DMSO-d₆) 8.69 (s,1H), 8.08 (d, J = 6.0 Hz, 1H), 7.40- 7.27 (m, 5H), 5.92 (d, J = 1.2 Hz,1H), 5.44 (d, J = 1.1 Hz, 1H), 3.23 (s, 3H), 3.12 (s, 3H)  62

white solid 144.7-146.3 ESIMS m/z 253 ([M + H]⁺) (CD₃OD) 8.72 (s, 1H),8.06 (d, J = 6.0 Hz, 1H), 6.96 (dd, J = 14.3, 1.6 Hz, 1H), 5.89 (dt, J =14.4, 7.2 Hz, 1H), 3.27 (s, 3H), 3.21 (s, 3H), 2.18 (ddd, J = 14.7, 7.3,1.4 Hz, 2H), 1.59-1.44 (m, 2H), 0.98 (t, J = 7.4 Hz, 3H)  63

Yellow solid 264.3-265.3 ESIMS m/z 317 ([M + H]⁺) DMSO-d₆) 8.72 (s, 1H),8.44 (d, J = 6.8 Hz, 1H), 7.56 (dd, J = 14.9, 1.8 Hz, 1H), 7.40 (d, J =8.7 Hz, 2H), 6.93 (d, J = 8.7 Hz, 2H), 6.86 (d, J = 14.9 Hz, 1H), 3.76(s, 3H), 3.25 (s, 3H), 3.12 (s, 3H)  64

yellow solid 222.4-224.4 ESIMS m/z 311 ([M + H]⁺) (DMSO-d₆) 8.74 (s,1H), 8.27 (d, J = 6.2 Hz, 1H), 8.04- 7.90 (m, 4H), 7.65- 7.49 (m, 3H),3.25 (s, 3H), 3.13 (s, 3H)  66

white solid 206.3-207.9 ESIMS m/z 374 ([M + H]⁺) (DMSO-d₆) 8.60 (t, J =6.0 Hz, 1H), 8.03 (d, J = 6.8 Hz, 1H), 7.43- 7.29 (m, 2H), 7.26-7.16 (m,J = 12.8, 5.9 Hz, 2H), 7.03-6.97 (m, 2H), 6.90 (dd, J = 8.5, 2.0 Hz,1H), 4.63 (d, J = 5.7 Hz, 2H), 3.79 (s, 3H), 3.75 (s, 3H)  67

white solid 168.6-169.1 ESIMS m/z 264 ([M + H]⁺) (DMSO-d₆) 8.81 (s, 1H),8.32 (d, J = 7.3 Hz, 1H), 7.34 (dd, J = 14.4, 6.6 Hz, 2H), 7.27-7.09 (m,2H), 5.30 (dd, J = 16.1, 1.5 Hz, 1H), 4.80 (dd, J = 9.2, 1.5 Hz, 1H),4.62 (d, J = 5.8 Hz, 2H)  68

white solid 231.6-233.1 ESIMS m/z 392 ([M + H]⁺) (CD₃OD) 8.11- 8.00 (m,2H), 7.94 (d, J = 6.3 Hz, 1H), 7.76-7.66 (m, 2H), 7.47 (t, J = 6.9 Hz,1H), 7.37- 7.25 (m, 1H), 7.20- 7.04 (m, 2H), 4.78 (s, 2H), 3.16 (s, 3H) 69

white solid 151.5-152.6 ESIMS m/z 318 ([M + H]⁺) (DMSO-d₆) 8.45 (t, J =5.7 Hz, 1H), 7.80 (d, J = 6.7 Hz, 1H), 7.37-7.10 (m, 4H), 5.68 (s, 1H),4.57 (d, J = 5.8 Hz, 2H), 2.15 (d, J = 33.7 Hz, 4H), 1.75- 1.47 (m, 4H) 70

white solid 138.9-140.2 ESIMS m/z 340 ([M + H]⁺) (DMSO-d₆) 8.63 (t, J =5.9 Hz, 1H), 8.02 (d, J = 6.6 Hz, 1H), 7.46-7.25 (m, 7H), 7.25-7.12 (m,2H), 5.89 (d, J = 0.9 Hz, 1H), 5.39 (d, J = 0.9 Hz, 1H), 4.62 (d, J =5.8 Hz, 2H)  71

white oil ESIMS m/z 306 ([M + H]⁺) (DMSO-d₆) 8.68 (t, J = 5.7 Hz, 1H),8.22 (d, J = 7.2 Hz, 1H), 7.39- 7.23 (m, J = 7.5 Hz, 2H), 7.23-7.05 (m,J = 15.2, 8.1 Hz, 2H), 6.88 (d, J = 14.4 Hz, 1H), 5.76 (dt, J = 14.4,7.2 Hz, 1H), 4.60 (d, J = 5.8 Hz, 2H), 2.06 (dd, J = 14.3, 7.1 Hz, 2H),1.48-1.29 (m, 2H), 0.89 (t, J = 7.3 Hz, 3H)  72

yellow solid 196.8-198.5 ESIMS m/z 370 ([M + H]⁺) (CD₃OD) 8.18 (d, J =6.8 Hz, 1H), 7.56 (dd, J = 14.8, 2.0 Hz, 1H), 7.50- 7.36 (m, 3H),7.35-7.24 (m, 1H), 7.14 (dd, J = 7.6, 6.4 Hz, 1H), 7.10- 7.03 (m, 2H),6.90 (d, J = 8.8 Hz, 2H), 6.68 (d, J = 14.7 Hz, 1H), 4.76 (s, 2H), 3.80(s, 3H)  73

white solid 207.5-209.0 ESIMS m/z 364 ([M + H]⁺) (DMSO-d₆) 8.76- 8.60(m, 1H), 8.21 (d, J = 6.8 Hz, 1H), 8.01-7.87 (m, 4H), 7.64-7.47 (m, 3H),7.10-7.45 (m, 4H), 4.65 (d, J = 6.2 Hz, 2H)  75

brown solid 229.2-231.3 ESIMS m/z 221 ([M + H]⁺) (CD₃OD) 8.58 (d, J =2.0 Hz, 1H), 8.49 (dd, J = 4.9, 1.5 Hz, 1H), 7.98 (d, J = 6.2 Hz, 1H),7.90-7.82 (m, 1H), 7.44 (dd, J = 7.9, 4.9 Hz, 1H), 4.98 (s, 2H)  76

off-white solid 179.2-181.1 ESIMS m/z 214 ([M + H]⁺) (DMSO-d₆) 7.83 (d,J = 6.8 Hz, 1H), 7.58 (s, 1H), 7.37 (s, 1H), 4.08-3.98 (m, 1H),3.84-3.71 (m, 2H), 3.63 (dd, J = 14.3, 7.3 Hz, 1H), 3.50 (dd, J = 13.5,7.8 Hz, 1H), 1.98-1.72 (m, 3H), 1.61- 1.43 (m, 1H)  77

white solid   140-142.8 ESIMS m/z 186 ([M + H]⁺) (DMSO-d₆) 8.57 (d, J =6.8 Hz, 1H), 8.15 (s, 1H), 7.98 (s, 1H), 4.06 (d, J = 7.4 Hz, 2H),2.72-2.54 (m, 1H), 1.47 (d, J = 6.6 Hz, 6H)  78

off-white solid 207.3-208.2 ESIMS m/z 202 ([M + H]⁺) (CDCl₃) 7.56 (d, J= 5.3 Hz, 1H), 3.99-3.91 (m, 2H), 3.68-3.62 (m, 2H), 3.48 (q, J = 7.0Hz, 2H), 1.17 (t, J = 7.0 Hz, 3H)  79

off-white solid 128.5-130.6 ESIMS m/z 190 ([M + H]⁺), 188 ([M − H]⁻)(CD₃OD) 7.52 (d, J = 5.8 Hz, 1H), 4.59 (s, 2H), 2.21 (s, 3H)  81

off-white solid 228-230 ESIMS m/z 318 ([M + H]⁺), (CD₃OD) 8.22 (s, 1H),7.54-7.25 (m, 5H), 5.26 (s, 2H), 3.71 (d, J = 6.4 Hz, 2H), 1.30 (s, 1H),0.68-0.53 (m, 2H), 0.50-0.33 (m, 2H)  82

off-white solid 159-161 ESIMS m/z 424 ([M + H]⁺) (CD₃OD) 8.72 (d, J =4.9 Hz, 1H), 7.52-7.41 (m, 4H), 7.36-7.31 (m, 2H), 7.28-7.23 (m, 4H),3.87 (d, J = 7.3 Hz, 2H), 1.41-1.33 (m, 1H), 0.71-0.63 (m, 2H),0.53-0.45 (m, 2H)  83

gum ESIMS m/z 293 ([M + H]⁺) (CD₃OD) 8.62 (d, J = 1.6 Hz, 1H), 8.51 (dd,J = 4.9, 1.3 Hz, 1H), 8.29 (d, J = 5.3 Hz, 1H), 7.90 (d, J = 7.8 Hz,1H), 7.45 (dd, J = 8.0, 4.9 Hz, 1H), 5.06 (s, 2H), 4.25 (q, J = 7.1 Hz,2H), 1.32 (t, J = 7.1 Hz, 3H)  84

off-white solid 137.1-138.8 ESIMS m/z 260 ([M − H]⁻) (Acetone-d₆) 8.18(s, 1H), 8.00 (d, J = 7.2 Hz, 1H), 4.64 (d, J = 6.3 Hz, 2H), 4.37 (q, J= 7.1 Hz, 2H), 2.23 (d, J = 4.4 Hz, 3H), 1.35 (t, J = 7.1 Hz, 3H)  86

yellow solid 181.8-183.5 ESIMS m/z 343 ([M + H]⁺) (CD₃OD) 8.28 (d, J =5.9 Hz, 1H), 8.22 (dd, J = 8.3, 1.4 Hz, 1H), 7.47 (dd, J = 8.0, 1.4 Hz,1H), 7.35-7.27 (m, 1H), 7.17-7.09 (m, 1H), 4.98 (s, 2H), 2.23 (s, 3H) 87

off-white solid 113.0-114.9 ESIMS m/z 297 ([M + H]⁺) (DMSO) 9.87 (s,1H), 9.38 (s, 1H), 8.34 (d, J = 5.9 Hz, 1H), 3.56 (d, J = 7.2 Hz, 2H),3.21 (d, J = 5.8 Hz, 2H), 1.58-1.41 (m, 2H), 1.40-1.09 (m, 5H), 0.88 (t,J = 6.8 Hz, 3H), 0.56-0.41 (m, 2H), 0.41- 0.29 (m, 2H)  88

off-white solid 205.6-207.5 ESIMS m/z 317 ([M + H]⁺) (CD₃OD) 8.25 (d, J= 6.0 Hz, 1H), 7.53 (d, J = 8.4 Hz, 2H), 7.16 (d, J = 8.3 Hz, 2H), 3.75(d, J = 7.3 Hz, 2H), 2.32 (s, 3H), 1.37- 1.26 (m, 1H), 0.67-0.59 (m,2H), 0.45 (q, J = 4.7 Hz, 2H)  89

off-white solid 146.0-147.6 ESIMS m/z 334 ([M + H]⁺), (DMSO-d₆) 9.96 (s,1H), 9.33 (t, J = 5.4 Hz, 1H), 8.59 (d, J = 1.7 Hz, 1H), 8.51 (s, 1H),8.50 (s, 1H), 7.76 (d, J = 8.0 Hz, 1H), 7.38 (dd, J = 7.6, 4.9 Hz, 1H),4.93 (s, 1H), 3.20 (dd, J = 12.7, 6.7 Hz, 2H), 1.55- 1.38 (m, 2H), 1.29(dd, J = 8.7, 5.4 Hz, 4H), 0.87 (t, J = 6.7 Hz, 3H)  90

off-white solid 178.2-180   ESIMS m/z 354 ([M + H]⁺⁾ (CD₃OD) 8.66 (d, J= 1.7 Hz, 1H), 8.52 (dd, J = 4.9, 1.6 Hz, 1H), 8.37 (d, J = 5.9 Hz, 1H),7.96-7.90 (m, 1H), 7.51 (d, J = 8.5 Hz, 2H), 7.47 (dd, J = 8.2, 5.2 Hz,1H), 7.15 (d, J = 8.3 Hz, 2H), 5.11 (s, 2H), 2.32 (s, 3H)  91

off-white solid 210.5-212.3 ESIMS m/z 374 ([M + H]⁺) (DMSO-d₆) 12.29 (s,1H), 10.59 (s, 1H), 8.64 (m, 2H), 8.52 (d, J = 4.8 Hz, 1H), 8.31 (dd, J= 8.3, 1.2 Hz, 1H), 7.83-7.77 (m, 1H), 7.52 (dd, J = 8.0, 1.2 Hz, 1H),7.43-7.31 (m, 2H), 7.12 (td, J = 7.9, 1.5 Hz, 1H), 4.98 (s, 2H)  92

off-white solid 100.2-101.8 ESIMS m/z 301 ([M − H]⁻) (CD₃OD) 8.43 (d, J= 7.4 Hz, 1H), 4.62 (s, 2H), 3.37 (t, J = 7.0 Hz, 2H), 2.22 (s, J = 5.7Hz, 3H), 1.61 (dd, J = 14.1, 7.1 Hz, 2H), 1.44-1.32 (m, 4H), 0.94 (t, J= 7.0 Hz, 3H)  93

off-white solid 188.8-190.2 ESIMS m/z 323 ([M + H]⁺) (CD₃OD) 8.27 (d, J= 5.9 Hz, 1H), 7.53 (d, J = 8.4 Hz, 2H), 7.16 (d, J = 8.2 Hz, 2H), 5.00(s, 2H), 2.32 (s, 3H), 2.24 (s, 3H)  95

pale yellow gum ESIMS m/z 256 ([M + H]⁺) (CDCl₃) 7.76 (d, J = 5.5 Hz,1H), 4.30 (dd, J = 13.8, 2.1 Hz, 1H), 4.18 (dd, J = 14.8, 7.6 Hz, 1H),3.87 (dd, J = 15.2, 6.9 Hz, 1H), 3.78 (dd, J = 14.4, 7.6 Hz, 1H), 3.57(dd, J = 13.8, 7.9 Hz, 1H), 2.65 (s, 3H), 2.20-2.06 (m, 1H), 2.01-1.85(m, 2H), 1.58 (ddd, J = 16.1, 12.5, 8.0 Hz, 1H)  96

white solid 119.8-121.9 ESIMS m/z 336 ([M + H]⁺), (DMSO-d₆) 11.22 (s,1H), 8.38 (s, 1H), 7.70 (s, 1H), 7.63 (dd, J = 13.0, 6.4 Hz, 1H), 7.33(t, J = 7.6 Hz, 2H), 4.11 (s, 1H), 3.96 (s, 1H), 3.80 (dd, J = 14.8, 6.9Hz, 1H), 3.74-3.59 (m, 2H), 2.02-1.91 (m, 1H), 1.91-1.75 (m, 2H), 1.63-1.51 (m, 1H)  97

white solid 134.5-136.5 ESIMS m/z 228 ([M + H]⁺) (CDCl₃) 7.72 (s, 1H),7.43 (d, J = 4.6 Hz, 1H), 3.63 (d, J = 7.4 Hz, 3H), 2.67 (s, 3H),2.29-2.12 (m, 1H), 0.98 (d, J = 6.7 Hz, 6H)  98

white solid 161.3-163   ESIMS m/z 308 ([M + H]⁺) (DMSO-d₆) 11.20 (s,1H), 8.49 (s, 1H), 7.80-7.54 (m, 2H), 7.33 (t, J = 7.5 Hz, 2H), 3.62 (d,J = 6.5 Hz, 2H), 2.08 (s, 1H), 0.87 (d, J = 6.7 Hz, 6H)  99

pale yellow solid 125.6-127.5 ESIMS m/z 296 ([M + H]⁺) (CDCl₃) 12.85 (s,1H), 7.97 (dd, J = 3.8, 1.2 Hz, 1H), 7.61 (dd, J = 4.9, 1.2 Hz, 1H),7.33 (d, J = 5.4 Hz, 1H), 7.14 (dd, J = 4.9, 3.8 Hz, 1H), 3.57 (d, J =7.5 Hz, 2H), 2.19-2.04 (m, 1H), 0.99 (d, J = 6.7 Hz, 6H) 100

off-white solid   109-110.4 ESIMS m/z 312 ([M + H]⁺), (CDCl₃) 8.00-7.93(m, 1H), 7.60 (dd, J = 4.8, 0.8 Hz, 1H), 7.56 (d, J = 5.6 Hz, 1H), 7.13(dd, J = 4.7, 4.0 Hz, 1H), 3.98-3.90 (m, 2H), 3.70-3.63 (m, 2H), 3.51(q, J = 7.0 Hz, 2H), 1.19 (t, J = 7.0 Hz, 3H) 101

off-white solid 116.8-117.8 ESIMS m/z 324 ([M + H]⁺) (CDCl₃) 8.20 (td, J= 7.8, 1.6 Hz, 1H), 8.02 (t, J = 7.6 Hz, 1H), 7.69 (d, J = 5.5 Hz, 1H),7.55 (dd, J = 13.1, 5.9 Hz, 1H), 7.32- 7.24 (m, 1H), 7.18 (dd, J = 11.7,8.3 Hz, 1H), 4.05-3.97 (m, 2H), 3.74- 3.66 (m, 2H), 3.50 (q, J = 7.0 Hz,2H), 1.19 (t, J = 7.0 Hz, 3H) 103

brown gum ESIMS m/z 242 ([M + H]⁺) (Acetone-d₆) 7.61 (d, J = 6.9 Hz,1H), 7.05-6.84 (m, 1H), 4.15-4.06 (m, 1H), 3.97 (dd, J = 13.7, 3.2 Hz,1H), 3.83 (dd, J = 14.9, 6.7 Hz, 1H), 3.68 (dd, J = 14.8, 6.9 Hz, 1H),3.51 (ddd, J = 20.0, 13.7, 7.3 Hz, 3H), 2.03-1.93 (m, 1H), 1.92-1.78 (m,2H), 1.60 (dd, J = 12.1, 8.1 Hz, 1H), 1.20 (t, J = 7.2 Hz, 3H) 104

gum ESIMS m/z 322 ([M + H]⁺) (Acetone-d₆) 7.70 (d, J = 6.7 Hz, 1H),7.53-7.42 (m, J = 6.9 Hz, 2H), 7.37- 7.27 (m, 1H), 7.21-7.06 (m, 2H),4.75 (d, J = 5.7 Hz, 2H), 4.11 (qd, J = 7.1, 3.2 Hz, 1H), 3.99 (dd, J =13.6, 3.2 Hz, 1H), 3.88- 3.79 (m, 1H), 3.69 (dd, J = 14.9, 6.9 Hz, 1H),3.55 (dd, J = 13.6, 7.8 Hz, 1H), 2.03-1.93 (m, 1H), 1.92- 1.80 (m, 2H),1.67-1.53 (m, 1H) 106

Off-white solid 88.8-91.7 ESIMS m/z 282 ([M + H]⁺) (CDCl₃) 7.30-7.25 (m,2H), 7.19 (d, J = 5.8 Hz, 1H), 7.08 (d, J = 3.1 Hz, 1H), 6.99 (dd, J =5.1, 3.5 Hz, 1H), 4.91 (d, J = 4.9 Hz, 2H), 3.57 (d, J = 7.5 Hz, 2H),2.17 (dt, J = 13.6, 6.8 Hz, 1H), 0.96 (d, J = 6.7 Hz, 6H) 107

brown gum ESIMS m/z 214 ([M + H]⁺) (CDCl₃) 7.14 (d, J = 5.9 Hz, 1H),3.65-3.50 (m, 4H), 2.16 (dt, J = 13.7, 6.9 Hz, 1H), 1.27 (t, J = 7.3 Hz,3H), 0.94 (d, J = 6.7 Hz, 6H) 108

brown solid 63-65 ESIMS m/z 230 ([M + H]⁺) (Acetone-d₆) 7.61 (d, J = 6.8Hz, 1H), 6.99 (s, 1H), 3.85 (t, J = 5.2 Hz, 2H), 3.62 (t, J = 5.2 Hz,2H), 3.54-3.42 (m, 4H), 1.20 (t, J = 7.2 Hz, 3H), 1.12 (t, J = 7.0 Hz,3H) 109

brown gum ESIMS m/z 310 ([M + H]⁺) (Acetone-d₆) 7.69 (d, J = 6.7 Hz,1H), 7.48 (t, J = 7.0 Hz, 1H), 7.37-7.27 (m, 1H), 7.20-7.05 (m, 2H),4.75 (d, J = 5.5 Hz, 2H), 3.88 (dd, J = 11.8, 6.6 Hz, 2H), 3.61 (dd, J =12.7, 7.7 Hz, 2H), 3.54-3.41 (m, 2H), 1.18-1.05 (m, 3H) 110

gum ESIMS m/z 298 ([M + H]⁺) (Acetone-d₆) 7.68 (d, J = 6.7 Hz, 1H), 7.57(s, 1H), 7.32 (dd, J = 5.1, 1.2 Hz, 1H), 7.12-7.04 (m, 1H), 6.95 (dd, J= 5.1, 3.5 Hz, 1H), 4.85 (d, J = 5.9 Hz, 2H), 3.88 (t, J = 5.2 Hz, 2H),3.63 (t, J = 5.2 Hz, 2H), 3.47 (q, J = 7.0 Hz, 2H), 1.12 (t, J = 7.0 Hz,3H)

Example 26 Evaluation of Fungicidal Activity: Leaf Blotch of Wheat(Mycosphaerella graminicola; Anamorph: Septoria tritici; Bayer CodeSEPTTR)

Wheat plants (variety Yuma) were grown from seed in a greenhouse in 50%mineral soil/50% soil-less Metro mix until the first leaf was fullyemerged, with 7-10 seedlings per pot. These plants were inoculated withan aqueous spore suspension of Septoria tritici either prior to or afterfungicide treatments. After inoculation the plants were kept in 100%relative humidity (one day in a dark dew chamber followed by two tothree days in a lighted dew chamber) to permit spores to germinate andinfect the leaf. The plants were then transferred to a greenhouse fordisease to develop.

The following table presents the activity of typical compounds of thepresent disclosure when evaluated in these experiments. Theeffectiveness of the test compounds in controlling disease wasdetermined by assessing the severity of disease on treated plants, thenconverting the severity to percent control based on the level of diseaseon untreated, inoculated plants.

In each case of Table II the rating scale is as follows

% Disease Control Rating  76-100 A 51-75 B 26-50 C  0-25 D Not Tested E

TABLE II One-Day Protectant (1DP) and Three-Day Curative (3DC) Activityof Compounds on SEPTTR at 100 ppm SEPTTR SEPTTR 100 100 PPM PPM Cmpd 1DP3DC 1 A A 2 A A 3 A A 4 C D 5 D D 6 D D 7 D D 8 C D 9 C D 10 C B 11 C D12 A A 13 A A 14 D D 15 D D 16 D D 17 B A 18 C B 19 C D 20 D D 21 A A 22A A 23 A A 24 A A 25 D D 26 D C 27 D D 28 B A 29 B A 30 D A 31 D A 32 AA 33 D B 34 A A 35 B B 36 B C 37 D D 38 D D 39 D A 40 D D 41 A A 42 E E43 C D 44 E E 45 E E 46 D D 47 C D 48 E E 49 E E 50 E E 51 E E 52 E E 53E E 54 E E 55 E E 56 C B 57 D D 58 A A 59 E E 60 E E 61 E E 62 E E 63 EE 64 E E 65 D D 66 D D 67 D B 68 E E 69 E E 70 F F 71 E E 72 E E 73 E E74 A B 75 C A 76 D B 77 C D 78 E E 79 E E 80 D B 81 C A 82 C C 83 C C 84E E 85 D D 86 C C 87 D B 88 D B 89 D C 90 D D 91 D D 92 A A 93 D B 94 DD 95 D B 96 D C 97 C C 98 D D 99 D A 100 E E 101 E E 102 E E 103 E E 104E E 105 D C 106 C C 107 D C 108 E E 109 E E 110 E E

What is claimed is:
 1. A compound of Formula I:

wherein R¹ is: H C₁-C₆ alkyl optionally substituted with 1-3 R⁴; C₁-C₆alkenyl optionally substituted with 1-3 R⁴; C₃-C₆ alkynyl optionallysubstituted with 1-3 R⁴; substituted phenyl, substituted benzyl, phenylor benzyl wherein substituents for the substituted phenyl or thesubstituted benzyl are selected from the group consisting of: 1-3 R⁵, orwith a 5- or 6-membered saturated or unsaturated ring system, or with a5-6 fused ring system, or with a 6-6 fused ring system each containing1-3 heteroatoms wherein each ring may be optionally substituted with 1-3R⁵, biphenyl or naphthyl optionally substituted with 1-3 R⁵;-(CHR6)_(m)OR⁷; -(CHR6)_(m)N(R9)R¹⁰; —C(═O)R⁸; —C(═S)R⁸; —S(O)₂R⁸;—C(═O)OR⁸; —C(═S)OR⁸; -(CHR6)_(m)N(R⁹)R¹⁰; —C(═O)N(R⁹)R¹⁰; or—C(═S)N(R⁹)R¹⁰; wherein m is an integer 1-4; R² is: H; or C₁-C₆ alkyloptionally substituted with R⁴; alternatively R¹ and R² may be takentogether to form: ═CR¹¹N(R¹²)R¹³; R³ is: C₁-C₆ alkyl optionallysubstituted with 1-3 R⁴, C₁-C₆ haloalkyl, C₁-C₆ hydroxyalkyl, C₂-C₆alkoxyalkyl, C₂-C₆ haloalkoxyalkyl, C₂-C₆ alkenyl optionally substitutedwith R¹⁴, C₂-C₆ haloalkenyl, C₃-C₆ alkynyl, substituted phenyl,substituted benzyl, phenyl or benzyl wherein substituents for thesubstituted phenyl or the substituted benzyl are selected from the groupconsisting of: 1-3 R⁵, or with a 5- or 6-membered saturated orunsaturated ring system, or with a 5-6 fused ring system, or with a 6-6fused ring system each containing 1-3 heteroatoms wherein each ring maybe optionally substituted with 1-3 R⁵, biphenyl or naphthyl optionallysubstituted with 1-3 R⁵; -(CHR⁶)_(m)OR⁷; -(CHR⁶)_(m)SR⁸; or—(CHR⁶)_(m)N(R⁹)R¹⁰; R⁴ is independently halogen, C₁-C₆ alkyl, C₁-C₄haloalkyl, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy, C₁-C₄ alkylthio, C₁-C₄haloalkylthio, amino, halothio, C₁-C₃ alkylamino, C₂-C₆ alkoxycarbonyl,C₂-C₆ alkylcarbonyl, C₂-C₆ alkylaminocarbonyl, hydroxyl, C₃-C₆trialkylsilyl, phenyl optionally substituted with 1-3 R⁵, or with a 5-or 6-membered saturated or unsaturated ring containing 1-3 heteroatomswherein each ring may be optionally substituted with 1-3 R⁵; R⁵ isindependently halogen, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₁-C₆ alkoxy, C₁-C₆haloalkoxy, C₁-C₆ alkylthio, C₁-C₆ haloalkylthio, halothio, amino, C₁-C₆alkylamino, C₂-C₆ dialkylamino, C₂-C₆ alkoxycarbonyl, C₂-C₆alkylcarbonyl, C₁-C₆ alkylsulfonyl, nitro, hydroxyl, or cyano; R⁶ is H,C₁-C₆ alkyl, C₁-C₆ alkoxy, C₁-C₆ alkoxycarbonyl, phenyl or benzylwherein each of the phenyl or the benzyl may be optionally substitutedwith 1-3 R⁵; R⁷ is H, C₁-C₈ alkyl, C₂-C₆ alkenyl, C₃-C₆ alkynyl, C₁-C₆haloalkyl, C₁-C₆ alkoxyalkyl, C₂-C₆ trialkylsilyl, C₂-C₆trialkylsilylalkyl C₂-C₆ alkylcarbonyl, C₁-C₆ alkoxycarbonyl,substituted phenyl, substituted benzyl, phenyl or benzyl whereinsubstituents for the substituted phenyl or the substituted benzyl areselected from the group consisting of: 1-3 R⁵, or with a 5- or6-membered saturated or unsaturated ring system, or with a 5-6 fusedring system, or with a 6-6 fused ring system each containing 1-3heteroatoms wherein each ring may be optionally substituted with 1-3 R⁵,biphenyl or naphthyl optionally substituted with 1-3 R⁵; R⁸ is H, C₁-C₆alkyl, C₂-C₆ alkenyl, C₃-C₆ alkynyl, C₁-C₆ haloalkyl, C₁-C₆ alkoxyalkyl,substituted phenyl, substituted benzyl, phenyl or benzyl whereinsubstituents for the substituted phenyl or the substituted benzyl areselected from the group consisting of: 1-3 R⁵, or with a 5- or6-membered saturated or unsaturated ring system, or with a 5-6 fusedring system, or with a 6-6 fused ring system each containing 1-3heteroatoms wherein each ring may be optionally substituted with 1-3 R⁵,biphenyl or naphthyl optionally substituted with 1-3 R⁵; R⁹ is H, C₁-C₆alkyl, C₁-C₆ haloalkyl, C₁-C₆ alkoxyalkyl, C₂-C₆ alkylcarbonyl,substituted phenyl, substituted benzyl, phenyl or benzyl whereinsubstituents for the substituted phenyl or the substituted benzyl areselected from the group consisting of: 1-3 R⁵, or with a 5- or6-membered saturated or unsaturated ring system, or with a 5-6 fusedring system, or with a 6-6 fused ring system each containing 1-3heteroatoms wherein each ring may be optionally substituted with 1-3 R⁵,biphenyl or naphthyl optionally substituted with 1-3 R⁵; R¹⁰ is H, C₁-C₆alkyl, C₁-C₆ haloalkyl, C₁-C₆ alkoxyalkyl, C₂-C₆ alkylcarbonyl, orbenzyl, wherein the benzyl may be optionally substituted with 1-3 R⁵;alternatively R⁹ and R¹⁰ may be taken together to form a 5- or6-membered saturated or unsaturated ring containing 1-3 heteroatomswherein each ring may be optionally substituted with 1-3 R⁵; R¹¹ is H orC₁-C₄ alkyl; R¹² is H, cyano, hydroxyl, C₁-C₄ alkyl, C₁-C₆ alkoxy,C₂-C₆, alkylcarbonyl, phenyl or benzyl wherein each of the phenyl or thebenzyl may be optionally substituted with 1-3 R⁵; or with a 5- or6-membered saturated or unsaturated ring system, or with a 5-6 fusedring system, or with a 6-6 fused ring system each containing 1-3heteroatoms wherein each ring may be optionally substituted with 1-3 R⁵,biphenyl or naphthyl optionally substituted with 1-3 R⁵; alternativelyR¹¹ and R¹² may be taken together to form a 5- or 6-membered saturatedor unsaturated ring containing 1-3 heteroatoms wherein each ring may beoptionally substituted with 1-3 R⁵; R¹³ is H, C₁-C₄ alkyl, C₁-C₆ alkoxy,C₂-C₆, alkylcarbonyl, phenyl or benzyl wherein each of the phenyl or thebenzyl may be optionally substituted with 1-3 R⁵; or with a 5- or6-membered saturated or unsaturated ring system, or with a 5-6 fusedring system, or with a 6-6 fused ring system each containing 1-3heteroatoms wherein each ring may be optionally substituted with 1-3 R⁵,biphenyl or naphthyl optionally substituted with 1-3 R⁵; andalternatively R¹² and R¹³ may be taken together to form a 5- or6-membered saturated or unsaturated ring containing 1-3 heteroatomswherein each ring may be optionally substituted with 1-3 R⁵. R¹⁴ isphenyl or benzyl wherein each of the phenyl or the benzyl may beoptionally substituted with 1-3 R⁵.
 2. A composition for the control ofa fungal pathogen including the compound of claim 1 and a phytologicallyacceptable carrier material.
 3. The composition of claim 2 wherein thefungal pathogen is Apple Scab (Venturia inaequalis), Leaf Blotch ofWheat (Septoria tritici), Leaf Spot of Sugarbeets (Cercospora beticola),Leaf Spots of Peanut (Cercospora arachidicola and Cercosporidiumpersonatum), and Black Sigatoka of Banana (Mycosphaerella fijiensis). 4.(canceled)
 5. The compound of claim 1, wherein: R¹ is: H; R² is H; R³ is—(CHR⁶)_(m)OR⁷, C₂-C₆ alkenyl, cyclopropylmethyl, or(tetrahydrofuran-2-yl)methyl, wherein m is an integer 1-4; R⁵ isindependently halogen, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₁-C₆ alkoxy, C₁-C₆haloalkoxy, C₁-C₆ alkylthio, C₁-C₆ haloalkylthio, halothio, amino, C₁-C₆alkylamino, C₂-C₆ dialkylamino, C₂-C₆ alkoxycarbonyl, C₂-C₆alkylcarbonyl, C₁-C₆ alkylsulfonyl, nitro, hydroxyl, or cyano; R⁶ is H,C₁-C₆ alkyl, C₁-C₆ alkoxy, C₁-C₆ alkoxycarbonyl, phenyl or benzylwherein each of the phenyl or the benzyl may be optionally substitutedwith 1-3 R⁵; and R⁷ is H, C₁-C₈ alkyl, C₂-C₆ alkenyl, C₃-C₆ alkynyl,C₁-C₆ haloalkyl, C₁-C₆ alkoxyalkyl, C₂-C₆ trialkylsilyl, C₂-C₆trialkylsilylalkyl C₂-C₆ alkylcarbonyl, C₁-C₆ alkoxycarbonyl, benzyl,phenyl or benzyl wherein each of the phenyl or the benzyl may beoptionally substituted with 1-3 R⁵, or with a 5- or 6-membered saturatedor unsaturated ring system, or with a 5-6 fused ring system, or with a6-6 fused ring system each containing 1-3 heteroatoms wherein each ringmay be optionally substituted with 1-3 R⁵, biphenyl or naphthyloptionally substituted with 1-3 R⁵.
 6. The compound of claim 5, whereinm is
 1. 7. The compound of claim 5, wherein R³ is selected from thegroup consisting of:

cyclopropylmethyl, and (tetrahydrofuran-2-yl)methyl.
 8. The compound ofclaim 1, wherein R¹ and R² are taken together to form: CR¹¹N(R¹²)R¹³. 9.The compound of claim 8, wherein R¹¹ is H, R¹² is —CH₃, and R¹³ is —CH₃.10. The compound of claim 1, wherein R³ is —(CHR⁶)_(m)OR⁷, R⁶ is H, m is1, and R⁷ is C₁-C₆ alkycarbonyl.
 11. The compound of claim 10, whereinR¹ and R² are each H, or R¹ and R² are taken together to form:═CR¹¹N(R¹²)R¹³.
 12. The compound of claim 1, wherein R³ is C₂-C₆alkenyl.
 13. The compound of claim 12, wherein R¹ and R² are each H, orR¹ and R² are taken together to form: ═CR¹¹N(R¹²)R¹³.
 14. The compoundof claim 1, wherein R³ is C₁-C₆ alkyl substituted with phenyl, whereinthe phenyl is substituted with 1-3 R⁵.
 15. The compound of claim 14,wherein R⁵ is halogen or C₁-C₆ alkoxy.
 16. The compound of claim 1,wherein R³ is C₁-C₆ alkyl and R¹ and R² are each H, or R¹ and R² aretaken together to form: ═CR¹¹N(R¹²)R¹³.
 17. The compound of claim 1,wherein R³ is cyclopropyl-methyl.
 18. The compound of claim 1, whereinR³ is —(CHR⁶)_(m)SR⁸, R⁶ is H, m is 1, and R⁸ is C₁-C₆ alkyl.
 19. Thecompound of claim 1, wherein R³ is C₁-C₆ alkyl optionally substitutedwith 1-3 R⁴, and R⁴ is a 5- or 6-membered saturated or unsaturated ringcontaining 1-3 heteroatoms.
 20. The compound of claim 1, wherein R³ isC₁-C₆ alkyl and R¹ is —C(═O)-thiophenyl.
 21. The compound of claim 1,wherein R³ is thiophenyl.